JP4031241B2 - Melt processable semi-crystalline block copolyimide - Google Patents

Description

【００５９】
【表２】

【００６０】
【表３】

【００６１】
【表４】

【００６２】
その他
ポリ（アミド酸）＝ポリアミド酸＝酸二無水物とジアミンとの最初の反応生成物であって、ポリイミドの前駆体。
【００６３】
【実施例】
（実施例１〜２１および比較例１〜４）
一般
ブロックコポリイミドは全て米国特許第５２０２４１２号に開示されている一般的合成法を用いて合成した。用いた酸二無水物およびジアミンは全て高純度ポリマー等級であった。無水Ｎ−メチル−２−ピロリジノン（ＮＭＰ）を溶媒として用いた。芳香族炭化水素混合物（Ａｒｏｍａｔｉｃ １５０、Ｅｘｘｏｎ）をこれらのコポリイミドを合成する際の共沸剤として用いた。比較例のためのランダムコポリイミドを合成するためにも同じモノマー、溶媒などを用いた。それらを用いる前に、全てのモノマーは、ジアミンについては４０〜５０℃、酸二無水物については１６０℃で終夜乾燥し、次いでびんに入れてこれを密封し、デシケーター中で保存した。以下に報告するＧＰＣ分子量は相対値である。
【００６４】
（実施例１）
柔軟性ブロック（「Ａ」ブロック）分子量が約１００００ｇ／モル（ＰＩとして）のキャッピングされていないＯＤＰＡ／ＡＰＢ−１３３（５０）／／ＢＰＤＡ／ＡＰＢ−１３４（５０）ブロックコポリイミドの合成を下記のとおりに行った。得られたサンプルはキャッピングされていないブロックコポリイミドであった。
【００６５】
撹拌機、窒素流入口、ディーンスタークトラップ／冷却器、および温度計（約２５０℃までの目盛付き）を備えた、乾燥した２５０ｍｌの４頚丸底フラスコを組み立て、反応順序開始の直前にヒートガンを用いて乾燥した。反応フラスコに８．１２９０ｇのＯＤＰＡおよびＮＭＰ（３０ｍｌ）を加え、緩やかな撹拌を開始した。ＡＰＢ−１３３（７．２３８９ｇ）をふた付き容器に秤量し、ＮＭＰ（３０ｍｌ）を加え、混合物をＡＰＢ−１３３が全て溶解するまで撹拌した。次いで、得られたジアミン溶液を、反応フラスコに緩やかに撹拌しながら加えた。ＮＭＰ（１０ｍｌ）を用いて容器を洗浄し、得られた洗液をフラスコに加えた。（工程＃３終了時の加えたＮＭＰ全容量（ｍｌ）は７０ｍｌで、混合物は約１７．５％が固体であった。）
得られた反応混合物を３０分間にわたって撹拌した。
【００６６】
ディーンスタークトラップをＡｒｏｍａｔｉｃ １５０液（Ｅｘｘｏｎ）で完全に満たした。アルミホイルを断熱材としてディーンスタークトラップの周りに巻き付けた。Ａｒｏｍａｔｉｃ １５０液（８ｍｌ）を容器中の反応混合物に加え、得られた反応混合物を１８０℃で約９０分間加熱した。反応温度を１８０℃で３時間維持し、その間、冷却器から凝縮液が一定速度で滴下し、水がディーンスタークトラップに回収された。
【００６７】
反応器内を通過する窒素気流を増大させ（約２倍）、フラスコの関係する部分をヒートガンで約５分間加熱してフラスコ内部に付着した凝結物を除去し、次いで窒素気流の速度を通常に戻した。反応フラスコが４５℃に冷えるまで加熱を停止し、次いで反応混合物を終夜６０〜７０℃に保持した。（以後のこの実施例に関係する全ての実施例では、この時点で、より低い設定で熱をかけて反応混合物を４５℃に保ち、後述するＢＰＤＡ／ＡＰＢ−１３４の追加を同じ日に４５℃の温度が確立された後に行った。）
【００６８】
ＢＰＤＡ（７．４９６４ｇ）ならびに１４ｍｌのＮＭＰ（洗浄液として）を反応混合物に緩やかに撹拌しながら加えた。ＡＰＢ−１３４（７．８７０８ｇ）を栓付き容器に秤量し、ＮＭＰ（２５ｍｌ）を加え、得られた混合物を溶液となるまで撹拌した。この溶液は滴下するまで栓をしたままにした。ＡＰＢ−１３４溶液を、滴下漏斗を用いて撹拌中の反応混合物に３０分かけて滴下した。滴下終了時に、ＮＭＰ（１０ｍｌ）を用いて栓付き容器を洗浄し、洗液を反応混合物に加えた。（この時点での反応混合物のおよその容量は１５０ｍｌであった。合計１１９ｍｌのＮＭＰを添加した。）滴下完了後、反応混合物を４５℃で１時間にわたって撹拌し、次いで室温でさらに終夜にわたって撹拌した。得られた中間生成物、ポリイミド／ポリアミド酸コポリマーを集め、乾燥した栓付き容器に保存した。
【００６９】
中間体ポリイミド／ポリアミド酸としてのこのサンプルに関するＧＰＣ分子量測定により、次の結果を得た：Ｍ_ｗ＝３５２ＫおよびＭ_ｎ＝１６２Ｋ。
【００７０】
前述の中間体ポリイミド／ポリアミド酸溶液サンプルを、ウェーハー上にスピンコーティングし、大気中１３５℃で３０分間予備焼き付けし、窒素中３５０℃で６０分間焼き付けし、ウェーハー支持体を腐食除去し、薄膜を水で洗浄し、次いで乾燥することによりポリイミド薄膜サンプルに変換して、特徴付け（characterization）試験に適した最終ポリイミド薄膜サンプルを得た。このポリイミド薄膜は１回目のＤＳＣスキャンで融点３６７℃を示した。
【００７１】
（注釈：実施例１では、ＡＰＢ−１３４添加後の最初の反応混合物はゲル化してゴム状の稠性を示した。これを固体分約２０重量％から約１５重量％に希釈してスピンコーティングがうまくいく溶液とした。）
（実施例２）
「Ａ」ブロックのサイズが１０ＫのＯＤＰＡ／ＡＰＢ−１３３（４０）／／ＢＰＤＡ／ＡＰＢ−１３４（６０）ブロックコポリイミド（キャッピングされていない）の合成を、実施例１の記載と類似の様式で、モノマーの量を次のとおりに調整して行った：ＯＤＰＡを８．１２７７ｇ；ＡＰＢ−１３３を７．２３７８ｇ；ＢＰＤＡを１１．３５０５ｇ；およびＡＰＢ−１３４を１１．６９９３ｇ。最初の反応混合物（ＢＰＤＡおよびＡＰＢ−１３４を添加し、４５℃に加熱した後）は粘性が高かった。これを２０ｍｌの無水ＮＭＰで希釈し、中等度の粘性の反応混合物として、これをうまくスピンコーティングして特徴付けのためのポリイミド薄膜サンプルを作成した（実施例１と同様）。このポリイミド薄膜は１回目のＤＳＣスキャンで融点３７５℃を示した。
【００７２】
中間体ポリイミド／ポリアミド酸としてのこのサンプルのＧＰＣ分子量分析により、次の結果を得た：Ｍ_ｗ＝３９３ＫおよびＭ_ｎ＝１８３Ｋ。
【００７３】
（実施例３）
「Ａ」ブロックのサイズが５ＫのＯＤＰＡ／ＡＰＢ−１３３（５０）／／ＢＴＤＡ／ＡＰＢ−１３４（５０）ブロックコポリイミド（キャッピングされていない）の合成を、実施例１の記載と類似の様式で、モノマーの量を次のとおりに調整して行った：ＯＤＰＡを８．３４６０ｇ；ＡＰＢ−１３３を７．０２１０ｇ；ＢＴＤＡを７．６１４４ｇ；およびＡＰＢ−１３４を７．７５４０ｇ。反応混合物（ＢＴＤＡおよびＡＰＢ−１３４を添加し、４５℃に加熱した後）を室温で週末の間にわたって撹拌し、中等度の粘性の溶液として、これを直接スピンコーティングして（実施例１と同様）特徴付けのためのポリイミド薄膜サンプルとした。このポリイミド薄膜は１回目のＤＳＣスキャンで低融点３５８℃および高融点３９１℃を示した。
【００７４】
中間体ポリイミド／ポリアミド酸としてのこのサンプルのＧＰＣ分子量分析により、次の結果を得た：Ｍ_ｗ＝９８ＫおよびＭ_ｎ＝５０Ｋ。
【００７５】
（比較例１）
「Ａ」ブロックのサイズが５ＫのＯＤＰＡ／ＡＰＢ−１３３（５０）／／ＰＭＤＡ／ＡＰＢ−１３３（５０）ブロックコポリイミド（キャッピングされていない）の合成を、実施例１の記載と類似の様式で、モノマーの量を次のとおりに調整して行った：ＯＤＰＡを８．３４６２ｇ；ＡＰＢ−１３３（第１のジアミンとして）を７．０２０１ｇ；ＰＭＤＡを５．８１３０ｇ；およびＡＰＢ−１３３（第２のジアミンとして）を８．６３５４ｇ。ポリイミド／ポリアミド酸反応混合物（第２のジアミンおよび第２の酸二無水物を添加し、４５℃に加熱した後）を通常の様式で終夜にわたって撹拌し、中等度の粘性の溶液として、これを直接スピンコーティングして（実施例１と同様）特徴付けのためのポリイミド薄膜サンプルとした。このポリイミド薄膜は１回目のＤＳＣスキャンで融点を示さなかった。
【００７６】
中間体ポリイミド／ポリアミド酸としてのこのサンプルのＧＰＣ分子量分析により、次の結果を得た：Ｍ_ｗ＝６４．８ＫおよびＭ_ｎ＝２９．７Ｋ。
【００７７】
（比較例２）
「Ａ」ブロックのサイズが５Ｋの６ＦＤＡ／ＡＰＢ−１３３（５０）／／ＢＰＤＡ／４，４′−ＯＤＡ（５０）ブロックコポリイミド（キャッピングされていない）の合成を、実施例１の記載と類似の様式で、モノマーの量を次のとおりに調整して行った：６ＦＤＡを９．５３６７ｇ；ＡＰＢ−１３３（第１のジアミンとして）を５．８３０８ｇ；ＢＰＤＡを８．５３４０ｇ；および４，４′−ＯＤＡ（第２のジアミンとして）を６．１１８８ｇ。ポリイミド／ポリアミド酸反応混合物（第２のジアミンおよび第２の酸二無水物を添加し、４５℃に加熱した後）を通常の様式で終夜にわたって撹拌し、中等度の粘性の溶液として、これを直接スピンコーティングして特徴付けのためのポリイミド薄膜サンプルとした。このポリイミド薄膜は１回目のＤＳＣスキャンで融点を示さなかった。
【００７８】
中間体ポリイミド／ポリアミド酸としてのこのサンプルのＧＰＣ分子量分析により、次の結果を得た：Ｍ_ｗ＝１１８ＫおよびＭ_ｎ＝３３．９Ｋ。
【００７９】
（比較例３）
「Ａ」ブロックのサイズが５ＫのＯＤＰＡ／ＡＰＢ−１３３（５０）／／ＤＳＤＡ／ＡＰＢ−１３４（５０）ブロックコポリイミド（キャッピングされていない）の合成を、実施例１の記載と類似の様式で、モノマーの量を次のとおりに調整して行った：ＯＤＰＡを８．３４５０ｇ；ＡＰＢ−１３３（第１のジアミンとして）を７．０２２４ｇ；ＤＳＤＡを７．９９７３ｇ；およびＡＰＢ−１３４（第２のジアミンとして）を７．３６９３ｇ。ポリイミド／ポリアミド酸反応混合物（第２のジアミンおよび第２の酸二無水物を添加し、４５℃に加熱した後）を通常の様式で終夜にわたって撹拌し、中等度の粘性の溶液として、、これを直接スピンコーティングして特徴付けのためのポリイミド薄膜サンプルとした。このポリイミド薄膜は１回目のＤＳＣスキャンで融点を示さなかった。
【００８０】
中間体ポリイミド／ポリアミド酸としてのこのサンプルのＧＰＣ分子量分析により、次の結果を得た：Ｍ_ｗ＝１１４ＫおよびＭ_ｎ＝５９．１Ｋ。
【００８１】
（比較例４）
「Ａ」ブロックのサイズが５ＫのＯＤＰＡ／ＡＰＢ−１３３（５０）／／ＢＰＤＡ／ＰＰＤ（５０）ブロックコポリイミド（キャッピングされていない）の合成を、実施例１の記載と類似の様式で、モノマーの量を次のとおりに調整して行った：ＯＤＰＡを８．３４５５ｇ；ＡＰＢ−１３３（第１のジアミンとして）を７．０２１０ｇ；ＢＰＤＡを１１．００８８ｇ；およびＰＰＤ（第２のジアミンとして）を４．３５８９ｇ。ポリイミド／ポリアミド酸反応混合物（第２のジアミンおよび第２の酸二無水物を添加し、４５℃に加熱した後）を通常の様式で終夜にわたって撹拌し、中等度の粘性の溶液として、、これを直接スピンコーティングして特徴付けのためのポリイミド薄膜サンプルとした。このポリイミド薄膜は１回目のＤＳＣスキャンで融点を示さなかった。
【００８２】
中間体ポリイミド／ポリアミド酸としてのこのサンプルのＧＰＣ分子量分析により、次の結果を得た：Ｍ_ｗ＝２３８ＫおよびＭ_ｎ＝１１８Ｋ。
【００８３】
（実施例４）
示差走査熱量測定（ＤＳＣ）を用いて（前述の実施例および比較例に示すとおり）、前述の実施例１〜３に示す３つのブロックコポリイミドサンプル、ならびに前述の比較例１〜４に一部を示した約１５〜２０の他のブロックコポリイミドの熱挙動を特徴付けた。各サンプルについて、２０℃／分の走査速度で室温から５００℃までのＤＳＣスキャンを１回行った。個々の実施例に記載のとおり、実施例１〜３のブロックコポリイミドサンプルはそれぞれＤＳＣ融点挙動を示し（すなわち、ＤＳＣトレースで特徴的な融点曲線を示し）、これらブロックコポリイミドそれぞれが半晶質の性質を有することが判明した。それとは著しく異なり、他の１５〜２０のサンプル群（比較例１〜４のサンプルを含む）ではＤＳＣ融点挙動を示すものはなく、それらが基本的に非晶質の性質を有することが明らかであった。
【００８４】
（実施例５）
柔軟性ブロック（「Ａ」ブロック）分子量が約１００００ｇ／モル（ＰＩとして）のキャッピングされたＯＤＰＡ／ＡＰＢ−１３３（５０）／／ＢＰＤＡ／ＡＰＢ−１３４（５０）ブロックコポリイミドの合成を、以下に記載のとおりに実施した。
【００８５】
全てのモノマーは、ジアミンについては４０〜５０℃で、二無水物については１６０℃で終夜乾燥し、次いでびんに入れてこれを密封し、デシケーター中で保存した。撹拌機、窒素流入口、ディーンスタークトラップ／冷却器、および温度計（約２５０℃までの目盛付き）を備えた、乾燥した２５０ｍｌの４頚丸底フラスコを組み立て、反応順序開始の直前にヒートガンを用いて乾燥した。反応フラスコに８．１２８８ｇのＯＤＰＡおよびＮＭＰ（３０ｍｌ）を加え、緩やかな撹拌を開始した。ＡＰＢ−１３３（７．２３７１ｇ）をふた付き容器に秤量し、ＮＭＰ（３５ｍｌ）を加え、混合物をＡＰＢ−１３３が全て溶解するまで撹拌した。次いで、得られたジアミン溶液を、反応フラスコに緩やかに撹拌しながら加えた。ＮＭＰ（５ｍｌ）を用いて容器を洗浄し、得られた洗液をフラスコに加えた。（上記工程終了時の加えたＮＭＰ全容量（ｍｌ）は７０ｍｌで、混合物は約１７．５％が固体であった。）得られた反応混合物を３０分間にわたって撹拌した。
【００８６】
ディーンスタークトラップをＡｒｏｍａｔｉｃ １５０液（Ｅｘｘｏｎ）で完全に満たした。アルミホイルを断熱材としてディーンスタークトラップの周りに巻き付けた。Ａｒｏｍａｔｉｃ １５０液（８ｍｌ）を容器中の反応混合物に加え、得られた反応混合物を１８０℃まで約９０分かけて加熱した。反応温度を１８０℃で３時間にわたって維持し、その間、冷却器から凝縮液が一定速度で滴下し、水がディーンスタークトラップに回収された。反応器内を通過する窒素気流を増大させ（約２倍）、フラスコの関係する部分をヒートガンで約５分間加熱してフラスコ内部に付着した凝結物を除去し、次いで窒素気流の速度を通常の初期速度に戻した。反応フラスコが４５℃に冷えるまで加熱を停止し、次いでより低い設定で熱をかけて反応混合物を４５℃に保った。ＢＰＤＡ（７．２７１０ｇ）ならびに１０ｍｌのＮＭＰ（洗浄液として）を反応混合物に緩やかに撹拌しながら加え、撹拌を１０分間続けた。次いで無水フタル酸（ＰＡ、０．２２６４ｇ）を、４ｍｌのＮＭＰを洗浄液に用いて反応混合物に加えた。ＡＰＢ−１３４（７．８７１０ｇ）を栓付き容器に秤量し、ＮＭＰ（３０ｍｌ）を加え、得られた混合物を溶液となるまで撹拌した。この溶液は滴下するまで栓をしたままにした。前述のＡＰＢ−１３４溶液を、滴下漏斗を用いて、撹拌中の反応混合物に３０分かけて滴下した。滴下終了時に、ＮＭＰ（１０ｍｌ）を用いて栓付き容器を洗浄し、洗液を反応混合物に加えた（この時点での反応混合物のおよその容量は１５０ｍｌであった。合計１１９ｍｌのＮＭＰを添加した）。滴下完了後、反応混合物を４５℃で１時間にわたって撹拌し、次いで室温でさらに終夜にわたって撹拌した。得られた中間生成物である、約２０重量％の固体を含むポリイミド／ポリアミド酸コポリマー溶液を集め、乾燥した栓付き容器に保存した。このポリイミド／ポリアミド酸反応混合物は中等度の粘性を有するものであった。これを以下に示す方法を用いて化学的にイミド化し、ＤＳＣ分析（前述の性質を提供するため）に向けたブロックコポリイミドのポリイミド粉末サンプルを得た。
【００８７】
用いた化学的イミド化法を以下に示す。窒素パージング（流入／流出口）および撹拌機を備えた化学的イミド化用の１００ｍｌ反応容器（フラスコ＋ヘッド）を組み立てた。（通常はこれらの２〜４つを同時に行った。）前述のブロックＰＩ／ＰＡＡコポリイミドサンプル（５０．０ｇ）を反応容器に加えた。２つの清浄で乾燥した１０ｍｌメスピペット（０．０２ｍｌの目盛付き）を用い、１つは無水酢酸を秤量し、もう１つはトリエチルアミンを秤量した。コポリイミドサンプルを中等度に撹拌しながら、指定された量（下記）の無水酢酸（ＡＡ）を反応混合物に加えた。反応混合物は混濁した。澄明で均質な反応混合物が得られるまで室温で撹拌を続けた。撹拌を続けながら、指定された量のトリエチルアミン（Ｅｔ_３Ｎ）を反応混合物に加えた。（トリエチルアミンを加えると直後に沈殿が生じた。）撹拌を室温で約６時間（または終夜）続け、この間、反応混合物中に生じた塊を定期的に崩した。
【００８８】
反応混合物を、電力をかけたワーリングブレンダー内のメタノール中に注ぎ、ポリイミドの沈殿を生じさせた。得られた沈殿を、ろ紙をつけたブフナー漏斗を用い、減圧濾過によって集めた。得られた固体を連続２夜にわたって乾燥した。第１夜はサンプルを減圧乾燥器中、１００℃で乾燥した。第２夜は約２００〜２１０℃に設定した減圧乾燥器中で最終乾燥を行った。最終乾燥後、大きい塊があれば全て崩して、妥当な均質性の粉末を得た。得られた粉末サンプルを分析および特徴付けに用いた。
【００８９】
実施例５で用いた化学的イミド化試薬の量を以下に示す。
【００９０】
【表５】

【００９１】
このポリイミドサンプルは、１回目のＤＳＣスキャンで融点３７４℃および融解熱１１．４Ｊ／ｇを示した。２回目および３回目のＤＳＣスキャン中には融点を示さず、したがって、回復可能な半晶性は示さなかった。
【００９２】
（実施例６〜１３）
以下に挙げた他の８つのキャッピングされたブロックコポリイミドの合成を、前述の実施例５と同様の様式で、使用する化学的イミド化試薬の量およびモノマーの量だけは次のとおりに調整して行った。
【００９３】
【表６】

【００９４】
【表７】

【００９５】
【表８】

【００９６】
（実施例１４）
実施例５〜１３からの粉末ポリイミドサンプルをそれぞれＤＳＣ分析にかけて、サンプルの融点、ガラス転移、および結晶化特性をその構造上の特徴と関連付けて決定した。１回目の５００℃までのＤＳＣ分析は、反復スキャンＤＳＣ分析中のサンプルの適当な上限温度（Ｔ_ｕｌ）を決定するために行った。このＴ_ｕｌは、それよりも高温では明らかな分解が起こる温度よりも低いが、全ての著明な転移（融解、ガラス転移など）の温度よりも高くなるように選択した。それぞれの場合に、反復スキャンＤＳＣのために元のサンプルは廃棄して代わりに新しいサンプルを用いた。
【００９７】
次いで、反復スキャンＤＳＣを次の様式で行った：
１）室温からＴ_ｕｌまで１０℃／分で１回目の加熱スキャン。
２）Ｔ_ｕｌから室温まで１０℃／分で低速冷却スキャン。
３）室温からＴ_ｕｌまで１０℃／分で２回目の加熱スキャン。
４）Ｔ_ｕｌから室温まで非制御の急冷スキャン。
５）室温から５００℃まで１０℃／分で３回目の加熱スキャン。
【００９８】
サンプルは、全て１回目のＤＳＣスキャン中に１回目のＤＳＣ融点挙動を示し（下記の１回目加熱）、これらのコポリイミドは半晶質であることが明らかとなった。Ａブロック対Ｂブロックの比が３０：７０または２０：８０のブロック組成物だけが所望の回復可能な半晶性を示すことが判明し、これらのサンプルではＤＳＣ融解挙動が３回のスキャン（１回目加熱、２回目加熱、および３回目加熱）全てで見られ、サンプルが溶融物から結晶化できることを示している。
【００９９】
これらのコポリイミドについて測定した特定の性質を以下に示す。
【０１００】
【表９】

【０１０１】
実施例１０〜１３のコポリイミドは１回目冷却スキャンおよび／または２回目加熱スキャン中にもかなりの大きさの結晶化ピークを示した。ピークは２８６〜３１８℃の範囲で見られ、融解熱は１３〜１８．１ジュール／グラムの範囲であった。
【０１０２】
（実施例１５）
選択されたブロックおよびランダムコポリイミドサンプルを、キャピラリーレオメーターを用い、溶融粘度について特徴付けた。測定は１００、２００、５００、１０００、および２０００秒^−１の５つの異なるずり速度で行った。通常は１つのずり速度で２回の測定を行い、その速度は通常は１０００秒^−１であった。代表的ブロックおよびランダムコポリイミドで得られた結果を以下に示す。
【０１０３】
【表１０】

【０１０４】
これらの溶融粘度測定により、ずり速度５００／秒で見かけ粘度１００Ｐａ．Ｓを示す、Ｍ_ｗ＝約６０ＫのＯＤＰＡ／ＡＰＢ−１３３／／ＢＰＤＡ／ＡＰＢ−１３４ブロックコポリイミドは、添加剤をまったく加えず溶融加工性であるために十分低い溶融粘度を有するという重要な結果が示された。
【０１０５】
（比較例５）
６モル％の無水フタル酸エンドキャップを有するＯＤＰＡ（２０）／ＢＰＤＡ（８０）／ＡＰＢ−１３３（２０）／ＡＰＢ−１３４（８０）ランダムコポリイミドの合成とＤＳＣ融解挙動および溶融粘度についての特徴付けを、前述の対応するブロックコポリイミドとの比較のために行った。このランダムテトラポリイミドの合成を下記のとおりに行った。
【０１０６】
全てのモノマーは、ジアミンについては４０〜５０℃で、酸二無水物については１６０℃で終夜にわたって乾燥し、次いでびんに入れてこれを密封してテープを巻き、デシケーター中で保存した。撹拌機、窒素流入口、ディーンスタークトラップ／冷却器、および温度計（約２５０℃までの目盛付き）を備えた、乾燥した２５０ｍｌの４頚丸底フラスコを組み立て、反応順序開始の直前にヒートガンを用いて乾燥した。反応フラスコにＮＭＰ（６０ｍｌ）を加え、緩やかな撹拌を開始した。撹拌中の反応混合物にＯＤＰＡ（８．２００６ｇ）およびＢＰＤＡ（２９．６３１６ｇ）を粉末で加えてスラリーとして、１０ｍｌのＮＭＰを洗浄液として用いて酸二無水物の粉末サンプルを反応フラスコに全て移した。ＡＰＢ−１３３（７．１６５４ｇ）およびＡＰＢ−１３４（３０．９１６０ｇ）のＮＭＰ（１７０ｍｌ）溶液を調製し、滴下の準備をした滴下漏斗に加えた。無水フタル酸（０．９２２７ｇ）およびＮＭＰ（洗浄液として１０ｍｌ）を撹拌中の反応混合物に加え、その後ただちに次の工程を行った。前述のジアミン溶液を撹拌中の反応混合物に１０〜２０分かけて加えた。追加のＮＭＰ（５ｍｌ）を洗浄液として加えた。（合計２９８ｍｌのＮＭＰを加えた。およその反応混合物容量は３７４ｍｌであった。）得られたポリアミド酸混合物を室温で終夜にわたって撹拌した。ポリアミド酸混合物のＧＰＣ分析により、次の分子量データを得た：Ｍ_ｎ＝９４．８ＫおよびＭ_ｗ＝１８０Ｋ。
【０１０７】
得られた中間体ポリイミド／ポリアミド酸混合物のサンプルを、６．３５ｍｌの無水酢酸および９．３９ｍｌのトリエチルアミンを用いて前述の化学的イミド化にかけ、このランダムコポリイミドの固体粉末サンプルを得た。このランダムコポリイミドはＤＳＣ分析により、１回目のＤＳＣスキャンで融点３２６℃および融解熱１１．９Ｊ／ｇであることが判明した。融点ＤＳＣ曲線は非常に広幅（相当するブロックコポリイミドと比べて）であった。２回目および３回目スキャンでは融点挙動は観察されず、このランダムコポリイミドは回復可能な半晶性を示さないことが明らかとなった。１回目のスキャンにおける融点挙動で証明されるとおり、最初の半晶性は有している。
【０１０８】
（比較例６）
ＢＰＤＡ／ＡＰＢ−１３４／ＰＡを９８／１００／４としたポリイミドの調製（８％の化学量論的な酸二無水物）
ＢＰＤＡ（１４．４１４ｇ、０．０４８９９モル）およびＤＭＡＣ（１７５ｍｌ）を混合してスラリーを形成した（ＢＰＤＡのＤＭＡＣへの溶解性は非常に低い）。撹拌しながらスラリーにＰＡ（０．２９６ｇ）を加え、次いで撹拌中のスラリーにＡＰＢ−１３４（１４．６１７ｇ、０．０５モル）を加えた。得られた混合物を室温で終夜にわたって撹拌してＢＰＤＡ／ＡＰＢ−１３４／ＰＡのポリアミド酸溶液として、以下の特徴を有していることが確認された。インヘレント粘度＝η_ｉｎｈ＝０．８６デシリットル／グラム（ｄｌ／ｇ）。
【０１０９】
前述のポリアミド酸溶液を以下の方法を用いて化学的にイミド化し、ＰＡでエンドキャッピングされたＢＰＤＡ／ＡＰＢ−１３４ホモポリイミドとした。前述のポリアミド酸溶液に撹拌しながらＴＥＡ（０．７２ｍｌ）およびＡＡ（１．０８ｍｌ）を加え、得られた混合物を３０℃で１８時間にわたって撹拌したところ、３０℃で約１時間後にサンプルのゲル化が認められた。得られたポリイミドを、ワーリングブレンダーに入れたメタノール中、５００ｍｌのメタノールに対しポリマー溶液約１０ｇの比を用いて単離した。濾過後、５００ｍｌのメタノールによる追加のワーリングブレンダー処理を行い、続いて窒素および減圧下、２００℃で一定の重量になるまで乾燥した。
【０１１０】
得られたポリイミドをＤＳＣで特徴付けた。ＤＳＣ試験は室温から最低４１０℃までの加熱スキャンを３回と、続いて各加熱スキャンの間の冷却スキャンにより実施した。各スキャンについてガラス転移温度（Ｔ_ｇ）、結晶化温度（Ｔ_ｃ）、および融点（Ｔ_ｍ）を測定した。結晶化温度は結晶化転移のＤＳＣ出力のピークとし、融点は融解転移のＤＳＣ出力のピークとした。このＢＰＤＡ／ＲＯＤＡホモポリイミドに関して、Ｔ_ｍ測定値は２回目加熱では４０３℃、１回目加熱では４０４℃であった。Ｔ_ｇ測定値は２００℃（２回目加熱）および２１８℃（３回目加熱）であり、Ｔ_ｃ（２回目加熱）測定値は２２２℃であった。このエンドキャッピングされたホモポリイミドは半晶質で回復可能な半晶性を示す（２回目および３回目熱スキャンで観察された融点により証明されている）が、その４００℃を超える融点は溶融加工性とするには高すぎる。したがってこれは比較例である。
【０１１１】
（実施例１６〜１９）
一般
本実施例は、選択された他のブロックコポリイミドが半晶質で、３９０℃未満の融点ならびに回復可能なＤＳＣ融点挙動を示すことを例示する。最初に合成して試験した他の約２５の、異なるモノマーおよびＡ：Ｂブロック比を有するキャッピングされたブロックコポリイミド組成物群から、次の４つがＤＳＣ（示差走査熱量測定）分析により半晶質ポリイミドであり、所望の融点範囲内で所望の回復可能なＤＳＣ融点挙動を示すことが判明した。回復可能なＤＳＣ融点挙動は、ポリマーサンプルが望まれるとおり溶融物から再結晶可能であることの重要な指標である。これらのブロックコポリイミドはそれぞれ、米国特許第５２０２４１２号に記載の合成法を用いてポリイミド／ポリアミド酸ブロックコポリマーの溶液として得られ、エンドキャッピングは通常無水フタル酸により化学量論上の９７％までであった。得られたＰＩ／ＰＡＡ溶液を化学的イミド化にかけて、加工および乾燥後にポリイミド粉末サンプルとして、、これをＤＳＣ分析にかけて以下に示す熱特性（Ｔ_ｇ、Ｔ_ｍ、およびＴ_ｃなど）を得た。
【０１１２】
【表１】

^ａ上の４つのブロックコポリイミドの合成を実施例１６〜１９に示す。
【０１１３】
（実施例１６）
柔軟性ブロック（「Ａ」ブロック）分子量が７５００ｇ／モル（ＰＩとして）のキャッピングされたＢＰＤＡ／ＡＰＢ−１３３（２０）／／ＢＰＤＡ／ＡＰＢ−１３４（８０）ブロックコポリイミドの合成を、以下に記載のとおりに実施した。サンプルを酸二無水物における化学量論の９７モル％とし、６モル％の無水フタル酸でエンドキャッピングした。合成を行うために以下の工程を実施した。
【０１１４】
全てのモノマーは、ジアミンについては４０〜５０℃で、酸二無水物については１６０℃で終夜乾燥し、次いでびんに入れてこれを密封し、デシケーター中で保存した。撹拌機、窒素流入口、ディーンスタークトラップ／冷却器、および温度計（約２５０℃までの目盛付き）を備えた、乾燥した５００ｍｌの４頚丸底フラスコを組み立て、反応順序開始の直前にヒートガンを用いて乾燥した。５００ｍｌのフラスコ内で最初の反応容量約８５ｍｌに温度計がつかるように装置を調節した。反応フラスコにＢＰＤＡ（７．９８９６ｇ）およびＮＭＰ（３０ｍｌ）を加え、緩やかな撹拌を開始した。
【０１１５】
ＡＰＢ−１３３（７．３７７１１ｇ）をふた付き容器に秤量し、ＮＭＰ（３５ｍｌ）を加え、混合物をＡＰＢ−１３３が全て溶解するまで撹拌した。次いで、得られたジアミン溶液を、反応フラスコに緩やかに撹拌しながら加えた。ＮＭＰ（５ｍｌ）を用いて容器を洗浄し、得られた洗液をフラスコに加えた。（上記工程終了時の加えたＮＭＰ全容量（ｍｌ）は７０ｍｌで、混合物は約１７．５％が固体であった。）得られた反応混合物を３０分間にわたって撹拌した。
【０１１６】
ディーンスタークトラップをＡｒｏｍａｔｉｃ １５０液（Ｅｘｘｏｎ）で完全に満たした。アルミホイルを断熱材としてディーンスタークトラップの周りに巻き付けた。Ａｒｏｍａｔｉｃ １５０液（８ｍｌ）を容器中の反応混合物に加え、得られた反応混合物を１８０℃まで約９０分かけて加熱した。反応温度を１８０℃で３時間維持し、その間、冷却器から凝縮液が一定速度で滴下し、水がディーンスタークトラップに回収された。反応器内を通過する窒素気流を増大させ（約２倍）、フラスコの関係する部分をヒートガンで約５分間加熱してフラスコ内部に付着した凝結物を除去し、次いで窒素気流の速度を通常の初期速度に戻した。反応フラスコが４５℃に冷えるまで加熱を停止し、次いでより低い設定で熱をかけて反応混合物を４５℃に保った。ＢＰＤＡ（２９．６３２７ｇ）ならびに１１０ｍｌのＮＭＰ（洗浄液として）を反応混合物に緩やかに撹拌しながら加え、撹拌を１０分間続けた。次いで無水フタル酸（ＰＡ、０．９２２７ｇ）を、１０ｍｌのＮＭＰを洗浄液に用いて反応混合物に加えた。ＡＰＢ−１３４（３０．９１５４ｇ）を栓付き容器に秤量し、ＮＭＰ（１００ｍｌ）を加え、得られた混合物を溶液となるまで撹拌した。この溶液は滴下するまで栓をしたままにした。前述のＡＰＢ−１３４溶液を滴下漏斗を用いて撹拌中の反応混合物に５〜１０分かけて滴下した。滴下終了時に、ＮＭＰ（８ｍｌ）を用いて栓付き容器を洗浄し、洗液を反応混合物に加えた。（この時点での反応混合物のおよその容量は３７４ｍｌであった。合計２９８ｍｌのＮＭＰを添加した。）滴下完了後、反応混合物を４５℃で１時間にわたって撹拌し、次いで室温でさらに終夜にわたって撹拌した。得られた中間生成物である、約２０重量％の固体を含むポリイミド／ポリアミド酸コポリマー溶液を集め、乾燥した栓付き容器に保存した。このポリイミド／ポリアミド酸反応混合物は中等度の粘性を有するものであった。これを以下に示す方法を用いて化学的にイミド化し、ＤＳＣ分析（前述の性質を提供するため）に向けたブロックコポリイミドのポリイミド粉末サンプルを得た。
【０１１７】
用いた化学的イミド化法を以下に示す。窒素パージング（流入／流出口）および撹拌機を備えた化学的イミド化用の１００ｍｌ反応容器（フラスコ＋ヘッド）を組み立てた。（通常はこれらの２〜４つを同時に行った。）前述のブロックＰＩ／ＰＡＡコポリイミドサンプル（５０．０ｇ）を反応容器に加えた。２つの清浄で乾燥した１０ｍｌメスピペット（０．０２ｍｌの目盛付き）を用い、１つは無水酢酸を秤量し、もう１つはトリエチルアミンを秤量した。コポリイミドサンプルを中等度に撹拌しながら、指定された量（下記）の無水酢酸（ＡＡ）を反応混合物に加えた。反応混合物は混濁した。澄明で均質な反応混合物が得られるまで室温で撹拌を続けた。撹拌を続けながら、指定された量のトリエチルアミン（Ｅｔ_３Ｎ）を反応混合物に加えた。（トリエチルアミンを加えると直後に沈殿が生じた。）撹拌を室温で約６時間（または終夜）続け、この間、反応混合物中に生じた塊を定期的に崩した。
【０１１８】
反応混合物を、電力をかけたワーリングブレンダー内のメタノール中に注ぎ、沈殿を生じさせた。得られた沈殿を、ろ紙をつけたブフナー漏斗を用い、減圧濾過によって集めた。得られた固体を連続２夜乾燥した。第１夜はサンプルを減圧乾燥器中、１００℃で乾燥した。第２夜は約２００〜２１０℃に設定した減圧乾燥器中で最終乾燥を行った。最終乾燥後、大きい塊があれば全て崩して、妥当な均質性の粉末を得た。得られた粉末サンプルを分析および特徴付けに用いた。
【０１１９】
実施例１６で用いた化学的イミド化試薬の量を以下に示す。
【０１２０】
【表１２】

【０１２１】
（実施例１７〜１９）
この一連の実施例（上記）における他の３つのキャッピングされたブロックコポリイミドの各合成を、前述の実施例１６と同様の様式で、ブロックＰＩ／ＰＡＡの合成に使用するモノマーの量および化学的イミド化試薬の量だけは次のとおりに調整して行った。
【０１２２】
【表１３】

【０１２３】
【表１４】

【０１２４】
（実施例２０）
実施例１６〜１９からの粉末ポリイミドサンプルをそれぞれＤＳＣ分析にかけて、サンプルの融点、ガラス転移、および結晶化特性をその構造上の特徴と関連付けて決定した。１回目のＤＳＣ分析は、反復スキャンＤＳＣ分析中のサンプルの適当な上限温度（Ｔ_ｕｌ）を決定するために行った。このＴ_ｕｌは、それよりも高温では明らかな分解が起こる温度よりも低いが、全ての著明な転移（融解、ガラス転移など）の温度よりも高くなるように選択した。それぞれの場合に、反復スキャンＤＳＣのために元のサンプルは廃棄して代わりに新しいサンプルを用いた。
【０１２５】
次いで、反復スキャンＤＳＣを次の様式で行った：
１）室温からＴ_ｕｌまで１０℃／分で１回目の加熱スキャン。
２）Ｔ_ｕｌから室温まで１０℃／分で低速冷却スキャン。
３）室温からＴ_ｕｌまで１０℃／分で２回目の加熱スキャン。
４）Ｔ_ｕｌから室温まで急冷スキャン。
５）室温から５００℃まで１０℃／分で３回目の加熱スキャン。
【０１２６】
この一連のブロックコポリイミドのＤＳＣ試験結果を以下に要約して示す。試験した多くのブロック組成物（約２５）のうちの少数だけがＤＳＣ分析により半晶質であると判明し、所望の回復可能なＤＳＣ融点挙動も示したのはさらに少なかった。さらに、これらのブロックコポリイミドは速い再結晶速度論を示すことが明らかとなり、これは大きな利点となりうる。これらのブロックコポリイミドのガラス転移温度（Ｔ_ｇ）は、先の実施例に記載のＯＤＰＡ／ＡＰＢ−１３３／／ＢＰＤＡ／ＡＰＢ−１３４ブロックコポリイミドサンプルまたは比較例に記載のランダムコポリイミドよりも幾分高い。
【０１２７】
これらのコポリイミドについて測定した特定の性質を以下に示す。
【０１２８】
【表１５】

【０１２９】
前述のキャッピングされたブロックコポリイミドサンプルはそれぞれ、回復可能なＤＳＣ融解挙動を示すことが判明し、約３８０℃で最も顕著であった（融解熱／ポリマー重量（ｇ）で測定）。この挙動は、これらのコポリイミドがそれぞれ、溶液から最初に得られる際に半晶質であり、さらに溶融加工性のＰＩに対して望まれるとおり溶融物から結晶化することを示すものである。（ＢＰＤＡ／ＡＰＢ−１３４を「Ｂ」ブロックとして含むこれらのブロックコポリイミドとは対照的に、対応するＢＰＤＡ／ＡＰＢ−１３４のホモポリイミドは融点が４００℃を超える−比較例６を参照。）
【０１３０】
（比較例７）
６モル％の無水フタル酸エンドキャップ（化学量論的な酸二無水物の９７％）を有するＢＰＤＡ／ＡＰＢ−１３３（２０）／ＡＰＢ−１３４（８０）ランダムコポリイミドの合成とＤＳＣ融解挙動および溶融粘度についての特徴付けを、前述の対応するブロックコポリイミドとの比較のために行った。このランダムテトラポリイミドの合成を下記のとおりに行った。
【０１３１】
全てのモノマーは、ジアミンについては４０〜５０℃で、酸二無水物については１６０℃で終夜乾燥し、次いでびんに入れてこれを密封してテープを巻き、デシケーター中で保存した。撹拌機、窒素流入口、ディーンスタークトラップ／冷却器、および温度計（約２５０℃までの目盛付き）を備えた、乾燥した２５０ｍｌの４頚丸底フラスコを組み立て、反応順序開始の直前にヒートガンを用いて乾燥した。反応フラスコにＮＭＰ（１００ｍｌ）を加え、緩やかな撹拌を開始した。撹拌中の反応混合物にＢＰＤＡ（１８．８１１９ｇ）を粉末で加えてスラリーとして、、１０ｍｌのＮＭＰを洗浄液として用いて酸二無水物の粉末サンプルを反応フラスコに全て移した。ＡＰＢ−１３３（３．６８７８ｇ）およびＡＰＢ−１３４（１５．４５８２ｇ）のＮＭＰ（６０ｍｌ）溶液を調製し、滴下の準備をした滴下漏斗に加えた。無水フタル酸（０．４６１４ｇ）およびＮＭＰ（洗浄液として４ｍｌ）を撹拌中の反応混合物に加え、その後ただちに次の工程を行った。前述のジアミン溶液を撹拌中の反応混合物に１０〜２０分かけて加えた。追加のＮＭＰ（８ｍｌ）を洗浄液として加えた。（合計１４９ｍｌのＮＭＰを加えた。およその反応混合物容量は１８７ｍｌであった。）
【０１３２】
得られたポリアミド酸混合物を室温で終夜にわたって撹拌した。ポリアミド酸混合物のＧＰＣ分析により、次の分子量データを得た：Ｍ_ｎ＝４９．２ＫおよびＭ_ｗ＝１４２Ｋ。
【０１３３】
得られた中間体ポリイミド／ポリアミド酸混合物のサンプルを、５．１９ｍｌの無水酢酸および７．６７ｍｌのトリエチルアミンを用いて前述の化学的イミド化にかけ、このランダムコポリイミドの固体粉末サンプルを得た。このランダムコポリイミドはＤＳＣ分析により、１回目のＤＳＣスキャンで融点３５２℃および融解熱２１．１Ｊ／ｇであることが判明した。融点ＤＳＣ曲線は非常に広幅（相当するブロックコポリイミドと比べて）であった。２回目のＤＳＣ加熱スキャンにおいて、融点は３４８℃であったが、融解熱は３．０Ｊ／ｇまで劇的に低下した。３回目加熱スキャンでは融点挙動はまったく認められなかった。したがって、このコポリイミドは、半晶質である（１回目のスキャンおよび２回目のスキャンにおける一部の融解挙動によって証明された）が、著しい回復可能な半晶性は示さないと特徴付けられた。
【０１３４】
（実施例２２〜２７）
これらの実施例は、下記の配列重合を達成するための別法を用いて合成した、回復可能な結晶性を有するブロックコポリイミドを例示する。６つのブロックコポリイミドを、ＯＤＰＡ、ＢＰＤＡ、ＡＰＢ−１３３、およびＡＰＢ−１３４を含む酸二無水物およびジアミン成分を用いて調製した。無水フタル酸エンドキャッピングは用いなかった。
【０１３５】
配列重合法を用いたが、これはまず一連のＯＤＰＡ／ＡＰＢ−１３３の可溶性オリゴマーポリイミドを対応するポリアミド酸の熱イミド化により製造することからなる。アミノ官能基が過剰のこれらの物質１つずつを、一定量のＢＰＤＡ／ＡＰＢ−１３４のポリアミド酸であって、化学量論量の９８％のＢＰＤＡを含むポリアミド酸と別々に混合した。次いで、全ての過剰アミノ基を消費するために必要な量のＢＰＤＡを加えることによってコポリマーを形成した。得られたコポリマーはＢＰＤＡ／ＡＰＢ−１３４の未変換のアミド酸鎖セグメントに連結されたＯＤＰＡ／ＡＰＢ−１３３のイミド化鎖セグメントで構成されていた。
【０１３６】
前述の部分的にイミド化されたブロックコポリマーを、無水酢酸およびトリエチルアミンを用いて全てイミド化されたブロックコポリイミドに完全に変換し、各コポリイミドをブレンダー内で過剰のアセトンにより粉末ポリイミド樹脂として単離した。生成物を２００℃で窒素および減圧下、一定重量になるまで乾燥した後、さらに特徴付けおよび有用性の証明を行った。詳細を以下に示す。
【０１３７】
ＯＤＰＡ／ＡＰＢ−１３３の調製−パートＡ
窒素充填グローブボックス内で、ＡＰＢ−１３３の溶液に下記の量のＯＤＰＡを撹拌しながら加えた。反応混合物を３時間にわたって撹拌し、次いでまず試薬等級のキシレン４０ｍｌを加え、還流下で撹拌後、イミド化の水がディーンスタークトラップに回収された。キシレンをストリッピング除去後、得られたオリゴマーイミドは可溶性であった。
【０１３８】
【表１６】

【０１３９】
ＢＰＤＡ／ＡＰＢ−１３４の調製−パートＢ
各オリゴマーイミド調製物（パートＡ）に対し、以下のポリアミド酸を製造した。窒素充填グローブボックス内で、一定量（２３．２８７ｇ）のＡＰＢ−１３４を２７７ｍｌの無水ＮＭＰに溶解した。この溶液に、２３．０６６グラムのＢＰＤＡを撹拌しながら２０分かけて加えた。混合物を終夜にわたって撹拌すると、澄明なポリアミド酸が得られた。
【０１４０】
ブロックコポリアミド酸／イミドの調製−パートＣ
パートＡの各ポリイミドオリゴマーサンプルをパートＢのポリアミド酸サンプルの１つと組み合わせた。下記に示すとおり、必要な量のＢＰＤＡをＮＭＰと共に加え、得られた反応混合物を４時間にわたって撹拌して、６つコポリアミド酸／イミド（実施例２２〜２７からのサンプル）を得た。
【０１４１】
【表１７】

【０１４２】
全てイミド化されたブロックコポリイミドの調製−パートＤ
パートＣの各コポリアミド酸／イミドを、そのそれぞれ１００グラムをトリエチルアミン１３ｍｌおよび無水酢酸９ｍｌと混合し、次いで反応混合物を窒素下で２４時間放置することにより、全てイミド化されたブロック（配列）コポリイミドに化学的に変換した。生成物をブレンダー内、アセトン中で沈殿させた。濾過後、生成物をブレンダー内で中等度の濾過により２回アセトン洗浄した。それぞれの場合に、樹脂を減圧乾燥器内で窒素下２００℃で一定の重量になるまで乾燥した。
【０１４３】
各サンプルをＤＳＣで分析した。ＤＳＣ分析はＭｅｔｔｌｅｒ ＴＡ ３０００システムおよび大きいアルミニウム皿を用いて実施した。ポリマーは窒素下で乾燥を保ち、分析の直前に秤量した。サンプル重量は３５から５０ｍｇの範囲で、４０ｍｇが好ましく、１０分の１ミリグラムの位まで秤量した。サンプルにＭｅｔｔｌｅｒ装置でキャップをし、皿のキャップに小さい孔を開けた後、ＤＳＣ分析を４００℃まで１０℃／分の速度で行った。皿と内容物をドライアイス中でただちに急冷した。次いでサンプルを窒素下で４００℃まで同じ速度で加熱し、再度急冷した。３回目の試行が望ましい場合には、同じ加熱速度および最高温度を適用した。
【０１４４】
【表１８】

【０１４５】
結果が明らかに示すとおり、これらのブロック（配列）コポリイミドでは独特の回復可能な結晶性の保持が見られる。
【０１４６】
【発明の効果】
以上説明したように、本発明によれば、高い熱安定性、溶融加工性および回復可能な結晶化度といった特性を同時に有するポリイミドコポリマーを提供することが可能となる。本発明にもとづくコポリマーは、溶融加工性であるための適当に低い溶融粘度を本質的に有するか、または特定の添加物を加えることによって溶融加工性であるための適当に低い溶融粘度を有するようにすることが可能である。また、コポリマーの融点およびガラス転移温度の調整は、その分子構成を変えることによって達成することが可能である。したがって、本発明のポリイミドコポリマーは溶融物の状態で加工され物品を形成することが可能であり、加工された物品は、押出し成形品、ファイバー、フィルムおよび成形製品などの所定の形状を有する。また、多くの場合、本発明のコポリマーは溶融重合を経て製造することも可能であるため、製造工程において冗長で費用のかかる溶媒リサイクルが不必要となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to selected block copolyimide compositions, each of which can be processed as a melt and is semi-crystalline. In a preferred embodiment, these block copolyimides exhibit crystallinity that can be recovered from the respective melt by cooling.
[0002]
[Prior art]
Polyimides, in particular, are thermally stable, inert properties (not normally soluble even in strong solvents), and high glass transition temperatures (T_gA useful group of polymers characterized by The prior art discloses that the precursor has heretofore been a polyamic acid that can ultimately be in an imidized form by either chemical treatment or heat treatment.
[0003]
Polyimide has always found numerous applications in many industries that require the above-mentioned properties, and its applications continue to increase dramatically, especially in the field of electronic devices, especially as dielectrics. .
[0004]
Various aspects regarding polyimides and copolyimides can be found in numerous publications. For example, see the following publications:
[0005]
Sroog, C.I. E. J. et al. Polymer Sci. : Part C, No. 16, 1191 (1967).
Sroog, C.I. E. J. et al. Polymer Sci. : Macromolecular Reviews, Volume 11, 161 (1976).
Polyimide, D. Wilson, H.C. D. Stenzenberger and P.M. M.M. Edited by Hergenroter, Blackie, USA: Chapman and Hall, New York, 1990.
[0006]
Several terms are defined below, but they have such high thermal stability that they can be processed in the melt, and in preferred embodiments when crystallized from the melt It is used in connection with the present invention for high performance polyimides that simultaneously have desirable properties such as exhibiting recoverable semi-crystallinity.
[0007]
The term “melt processable polyimide” means that the polyimide is processed in the melt to form a shaped article without undergoing any significant degradation (eg, extrusion into pellets, etc.). Means that the polyimide has a sufficiently high thermal oxidation stability and a sufficiently low melt viscosity at temperatures above the melting point of the polyimide.
[0008]
The term “DSC” is an abbreviation for differential scanning calorimetry, a widely used thermal analysis technique for accurately measuring various thermal properties of samples, including melting point, crystallization point and glass transition temperature. . The abbreviation “DSC” is used in the text below. The following definitions of slow crystallization rate, intermediate crystallization rate and fast crystallization rate and related terms are as follows when DSC analysis is performed under scanning such as slow cooling, rapid cooling, reheating during DSC analysis. Based on the behavior of a given sample (see below for details).
[0009]
The term “slow crystallization rate” means that for a given copolyimide sample, when subjected to DSC analysis, when the sample is slowly cooled from its melt (ie, cooled at 10 ° C./min). It means that the crystallization rate shows essentially no crystallization but shows a crystallization peak upon subsequent reheating. Furthermore, crystallization does not occur during rapid cooling.
[0010]
The term “intermediate crystallization rate” means that for a given copolyimide sample, when subjected to DSC analysis, the sample shows some crystallization upon slow cooling, and also when reheated after slow cooling. It means a crystallization speed that shows some crystallization. Furthermore, there is no strong evidence that crystallization occurs during quenching.
[0011]
The term “fast crystallization rate” means that for a given copolyimide sample, when subjected to DSC analysis, the sample exhibits a crystallization peak in both slow cooling and quenching, and an observable crystallization peak. Means a crystallization rate not observed during subsequent reheating after slow cooling of a given sample. After quenching, some crystallization may be seen during reheating.
[0012]
The term “polymer melt” means that the polymer exists as a melt in a liquid or substantially liquid state. If the polymer is crystalline or semicrystalline, the polymer melt will have its melting point (T_m) Must be above temperature.
[0013]
The terms “recoverable semi-crystallinity” and / or “recoverable crystallinity” refer to behavior associated with semi-crystalline polymers or crystalline polymers. These occur in particular when the polymer exhibits a melting point in a reheat DSC scan when heated to a temperature above the melting point of the polymer and subsequently slowly cooled to a temperature well below the melting point of the polymer. It means the following behavior. (If no melting point is observed during reheat DSC scan, the polymer does not show recoverable crystallinity._mAt temperatures below, but T_gThe longer it is placed at a higher temperature, the more likely the sample will crystallize. )
[0014]
The term “semi-crystalline polymer” means a polymer that exhibits at least some crystalline properties and has partial, but not complete, crystallinity. Most or all of the known polymers with crystalline properties are semi-crystalline, but they also have at least some amorphous properties and thus are not fully crystalline. (Thus, the term crystalline polymer is technically a misnomer in most or all of the situations in which it is used, but is often used nonetheless.)
[0015]
The term “uncapped copolyimide (random or block)” means a reaction product consisting of a combination of monomers without capping agent (eg, acid dianhydride and diamine).
[0016]
Some of the significant advantages of melt processing semi-crystalline polyimides with recoverable crystallinity according to the present invention include solvent-free processing, resulting in redundant and costly solvent recycling. Becomes unnecessary and can be omitted. High thermal stability is not only essential for processing with melts at temperatures above 350 ° C., but is also necessary for polyimides used in high temperature applications. Semicrystalline polyimides are often highly desirable compared to other similar polyimides that are amorphous. The former, in contrast to the latter, often have better mechanical properties (eg, especially higher modulus), the ability to be used at higher temperatures without property failure (eg better soldering) Having solder resistance, elastic modulus retention), higher solvent resistance, higher creep viscosity (eg, less change to strain of film or other structure over time), and lower coefficient of thermal expansion This is because it exhibits excellent properties.
[0017]
In order for a semi-crystalline polyimide to be considered melt processable, the polyimide has a practical limit of melt processing of about 385 ° C., both due to equipment capabilities / limitations and avoiding any significant thermal decomposition of the polyimide. It must have a melting point below the temperature range of 395 ° C. Furthermore, the polyimide must have a sufficiently low melt viscosity (ie, up to about 10 depending on the melting temperature of the polymer and the shear rate of the melt processing equipment).⁸Poise (this is 10⁷Less than or equal to Pascal / sec), but preferably at most 10⁴Poise (this is 10³Less than or equal to Pascal / sec) Although copolymerization can be used to lower the melting temperature of a polymer (eg, polyimide), copolymerization usually results in a loss of crystallinity. Prior art compositions are capable of simultaneously maintaining a high degree of semi-crystallinity in the copolymer composition while maintaining the melting point (T_mThe reduction in s) could not be suitably achieved. In the compositions of the present invention, both a suitable melting temperature and a high degree of semi-crystallinity are achieved by carefully choosing the comonomer and capping agent and their relative amounts in the block copolyimide composition. The
[0018]
Various polyimides that exhibit melting points in the initial DSC thermal scan and are believed to have crystalline properties thereby are disclosed in US Pat. No. 4,923,968 (Kunimune, Chisso Corporation). The copolyimide disclosed in this patent can be crystalline or semi-crystalline until heated to a temperature above its melting point, but we can recover the copolyimide disclosed in this patent. It has not been confirmed to show a high degree of recrystallization. In fact, these copolyimides are probably considered to be substantially amorphous when cooled from the melt. Furthermore, most or all of the copolyimides disclosed in this patent cannot be melt processed because they have a melting point, molecular weight (melt viscosity) and / or melt viscosity that are too high for melt processability. Further, no end capping process is taught to moderate polymerization and improve melt processability.
[0019]
The selected block copolyimides of the present invention, in a preferred embodiment, are those copolyimides that have important essential properties simultaneously (high thermal stability, melt processability and recoverable crystallinity). Overcoming the shortcomings of prior art compositions. Accordingly, the copolyimide of the present invention can be processed in the form of a melt to form an article. The processed article can have a predetermined shape, such as an extrudate, fiber, film and molded product, which is composed of semi-crystalline copolyimide. In many cases, the copolyimide of the present invention can be produced in a molten state (via melt polymerization).
[0020]
Some properties of polymers are segmented or block copolymers in which each segment or block provides a particular desired characteristic or property (the terms “block” and “segment” with respect to copolymer are used synonymously herein. ) Is best controlled and diversified. A typical example is the case of a styrene / butadiene block copolymer, of the two main components of toughness, stiffness and elasticity, where the styrene block provides rigidity and the butadiene block provides elasticity. The desired mechanical properties achieved by block polymerization of styrene and butadiene blocks are not the case with random polymerization, despite the fact that the empirical chemical formula, molecular weight, and other parameters remain constant in each case. It cannot be realized.
[0021]
Thus, in the case of polyimides, many attempts have been made to reproduce this block concept in order to control its properties to meet the requirements of a given specific application. However, all previous attempts have been partially or totally unsuccessful. Some properties of polyimide that are believed to be the cause of the failure of these attempts are described below.
[0022]
First, polyimides are useful because they are usually insoluble in most or all common solvents. Therefore, polyimide has high solvent resistance. However, this beneficial property itself is a burden on the process of applying highly insoluble polyimides, for example in the form of coatings. Thus, the most common technique in the prior art for applying polyimide as a coating is to use a solution of each poly (amidic acid) that is much more soluble and then respond to the polyamic acid by thermal or chemical means after application. It is a method of converting to imide. Another method that is equally useful in the preparation of segmented polyimides is to use soluble oligomers or precursors (of many esters) with terminal functional groups such as isocyanates, epoxides, acetylenic and ethylenically unsaturated functionalities, and then A method of extending or crosslinking it. However, these functional groups cause a decrease in thermal oxidation stability and may generally cause deterioration of the properties of the polymer.
[0023]
Second, the unique characteristics of poly (amic acid), which is actually the reaction product of carboxylic dianhydride with diamine, is that their components (diamine and dianhydride) drive dynamic equilibrium. In contrast, polyimides typically do not have such a change because they are permanently in a state of dynamic equilibrium, where the position is continuously compatible depending on the factors. The equilibrium of poly (amic acid) is C.I. C. Walker, J .; Polym. Sci. Part A: Polym. Chem. Ed. , 26, 1649 (1988). The re-equilibration of the binary poly (amic acid) mixture is Ree, D.D. Y. Yoon, W .; Volksen; "bicomponent poly (amic acid) miscible behavior of the mixture and re-equilibration (Miscibility Behavior and Reequilibration of Binary Poly (Amic Acid) Mixture)", Polymeric Materials; Science & Engineering Proceedings of ACS Division of Polymeric Materials; V60; P. 179-182; Spring 1989. On the other hand, the equilibrium in the case of aromatic polyimide is described in, for example, Takekoshi, T .; , “Synthesis of Polyimideides by Transimideization Reaction”, preprints of symposium on Recipients in Othr. Of Polymer Chemistry, Am. Chem. Soc. San Diego, CA, Jan. Strict conditions as described in 1990 are required.
[0024]
Due to the aforementioned dynamic equilibrium of poly (amic acid), generally two different polyamic acids are reacted together and simultaneously or subsequently imidized to produce a segmented copolyimide having two distinct segments. It is impossible to synthesize.
[0025]
In US Pat. No. 5,202,212, a polyimide copolymer oligomer precursor that is soluble in a polar solvent, a method of producing a polyimide precursor, and a first imidized segment (block) and a second imidized segment (block), A method of producing a block polyimide copolymer is disclosed in which the first imidized segment consists of a given polyimide precursor. The block polyimide copolymer produced by the method disclosed in this patent has an amine and anhydride rearrangement in (1) the first imidized segment and (2) the first imidized segment and the second It has the property of being substantially hindered between the amidic acid segment (which is the precursor of the second imidized segment). However, there is no teaching in this patent how block copolyimides can be melt processable and / or exhibit recoverable recrystallization.
[0026]
[Problems to be solved by the invention]
In view of the foregoing considerations, a high performance polyimide with high thermal stability, which can be processed in a melt (melt processability) and recovery as defined herein in a preferred embodiment There is a long-felt need for polyimides that exhibit possible semi-crystalline properties. However, such demands are not satisfied by the current state-of-the-art polyimide technology. The present invention thus provides a solution to these long-needed needs.
[0027]
[Means for Solving the Problems]
One embodiment of the present invention is a segmented melt processable semicrystalline polyimide copolymer comprising a first imidized segment and a second imidized segment, the copolymer comprising the following steps:
(A) preparing a first amic acid segment,
The first amic acid segment is a precursor of the first imidized segment, and a first amic acid segment having two identical terminal portions selected from the group consisting of an acid anhydride and an amine is obtained. A reaction product obtained by reacting the first acid dianhydride with the first diamine at a molecular ratio of
The combination of the first acid dianhydride and the first diamine to form the first amic acid segment is 4,4'-oxydiphthalic anhydride (ODPA) and 1,3-bis (3- In combination with (aminophenoxy) benzene (APB-133), (3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,3-bis (3-aminophenoxy) benzene (APB- 133), a combination of pyromellitic dianhydride (PMDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), (2,2'-bis- (3,4-di) Carboxyphenyl) hexafluoropropane dianhydride (6FDA) in combination with 1,3-bis (3-aminophenoxy) benzene (APB-133), 3,3 ', 4,4'-diphenyls Combination of hontetracarboxylic dianhydride (DSDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), and (2,2'-bis- (3,4-dicarboxyphenyl) A step selected from the group consisting of a combination of hexafluoropropane dianhydride (6FDA) and 1,3-bis (4-aminophenoxy) benzene (APB-134);
(B) imidating the first amic acid segment to form a first imidized segment;
(C) reacting the first imidized segment with one or more reactants,
The one or more reactants include the group consisting of (1) a second acid dianhydride and a second diamine, and (2) a second amic acid segment and a second acid dianhydride and a second diamine. Selected from the group consisting of linking monomers selected from
The choice of linking monomer between diamine and dianhydride in (2) above is selected by selecting the linking monomer necessary to produce a polyimide / polyamic acid copolymer having a total stoichiometry of about 100%. The first imidized segment reacts with the one or more reactants to form a segmented polyimide / polyamic acid copolymer comprising a first imidized segment and a second amic acid segment. And
The second amic acid segment is linked to the first imidized segment via an amide group having a carbon-nitrogen bond;
The combination of the second acid dianhydride and the second diamine to form the second amic acid segment is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), respectively. And 1,3-bis (4-aminophenoxy) benzene (APB-134), and (3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) and 1,3-bis A step selected from the group consisting of a combination with (4-aminophenoxy) benzene (APB-134);
(D) imidating the second amic acid segment to form a second imidized segment, thereby forming a segmented melt-processable semicrystalline polyimide copolymer
It is prepared by these.
[0028]
In the present invention, at least one of the first imidized segment and the second imidized segment containing the imide repeating unit, which imparts a semi-crystallinity to the corresponding homopolyimide containing the imide repeating unit, is essential, Is done. Furthermore, the first imidized segment is soluble in one or more reaction solvents at the reaction temperature relative to the segmented polyimide / polyamic acid copolymer described above.
[0029]
In a preferred embodiment, the copolyimides of the present invention have stoichiometric amounts in the range of 93% to 98%, exhibit melting points in the range of 330 ° C. to 395 ° C., and recovery as determined by DSC analysis. Shows possible crystallinity. Preferably, the copolyimides of the present invention have a melting point below 385 ° C, more preferably below 380 ° C.
[0030]
As used herein, the term “stoichiometric amount” expressed as a percentage refers to the total molar amount of acid dianhydride relative to the total molar amount of diamine incorporated into a given polyimide. means. If the total molar amount of dianhydride is equal to the total molar amount of diamine, the stoichiometric amount is 100 percent. If these two components are not equal, either the total amount of diamine or the total amount of dianhydride is present in a greater amount, where the stoichiometric amount is the component present in the lower amount (diamine or acid dianhydride). Product) is expressed as mole percent of such components present in large amounts. As an example, if a polyimide sample is obtained from a blend of 0.98 moles of acid dianhydride and 1.00 moles of diamine, the diamine is present in a greater amount, with a stoichiometric amount of 98% It is.
[0031]
If the stoichiometric amount is less than 93%, the copolyimide has insufficient mechanical properties. When the stoichiometric amount exceeds 98%, the copolyimide has a melting point that is too high for melt processability and does not exhibit feasible and / or recoverable crystallinity.
[0032]
As used herein, the term “end capping” means a monofunctional component (drug) and includes, but is not limited to, phthalic anhydride, naphthalic anhydride and aniline. They capping the copolyimide to moderate polymerization and increase the thermoplasticity of the final melt polymerization product. End capping is generally carried out to 100% so that the total moles of anhydride functionality is equal to the total moles of amine functionality. Phthalic anhydride and naphthalic anhydride are preferred end-capping components in cases where the diamine is present in a greater molar amount than the acid dianhydride. Aniline is a suitable end-capping component in cases where the acid dianhydride is present in a larger molar amount than the diamine. The proportion of end-capping component required to achieve 100% end-capping is equal to twice the value of 100 times (1-stoichiometry). As an example, for a copolyimide having 95% stoichiometric amount (excess of diamine) with 100% end-capping treatment, the total number of moles of end-capping agent is 10 mole percent of the total number of moles of diamine. (I.e., 10 moles of endcapping agent per 100 moles of diamine).
[0033]
In another embodiment, the present invention is a segmented polyimide / polyamic acid copolymer comprising a first imidized segment and a second amic acid segment, the copolymer comprising the following steps:
(A) preparing a first amic acid segment,
The first amic acid segment is a precursor of the first imidized segment, and a first amic acid segment having two identical terminal portions selected from the group consisting of an acid anhydride and an amine is obtained. A reaction product obtained by reacting the first acid dianhydride with the first diamine at a molecular ratio of
The combination of the first acid dianhydride and the first diamine to form the first amic acid segment is 4,4'-oxydiphthalic anhydride (ODPA) and 1,3-bis (3- In combination with (aminophenoxy) benzene (APB-133), (3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,3-bis (3-aminophenoxy) benzene (APB- 133), a combination of pyromellitic dianhydride (PMDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), (2,2'-bis- (3,4-di) Carboxyphenyl) hexafluoropropane dianhydride (6FDA) in combination with 1,3-bis (3-aminophenoxy) benzene (APB-133), 3,3 ', 4,4'-diphenyls Combination of hontetracarboxylic dianhydride (DSDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), and (2,2'-bis- (3,4-dicarboxyphenyl) A step selected from the group consisting of a combination of hexafluoropropane dianhydride (6FDA) and 1,3-bis (4-aminophenoxy) benzene (APB-134);
(B) imidating the first amic acid segment to form a first imidized segment;
(C) reacting the first imidized segment with one or more reactants,
The one or more reactants include the group consisting of (1) a second acid dianhydride and a second diamine, and (2) a second amic acid segment and a second acid dianhydride and a second diamine. Selected from the group consisting of linking monomers selected from
By selecting the linking monomer required to produce a polyimide / polyamic acid copolymer having a total stoichiometry of about 100% is selected for the linking monomer between the diamine and dianhydride in (2) above. Under the conditions selected, the first imidized segment reacts with the one or more reactants to form a segmented polyimide / polyamic acid copolymer comprising a first imidized segment and a second amic acid segment. Forming,
The second amic acid segment is linked to the first imidized segment via an amide group having a carbon-nitrogen bond;
The combination of the second acid dianhydride and the second diamine to form the second amic acid segment is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), respectively. And 1,3-bis (4-aminophenoxy) benzene (APB-134), and (3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) and 1,3-bis A process selected from the group consisting of combinations with (4-aminophenoxy) benzene (APB-134).
It is prepared by these. This segmented polyimide / polyamic acid copolymer is a precursor to the aforementioned segmented polyimide copolymer.
[0034]
DETAILED DESCRIPTION OF THE INVENTION
A novel segmented (block) copolyimide having an appropriate molecular configuration is defined herein as a copolyimide that is semicrystalline, can be crystallized from a melt, and is melt processable. Is done. Furthermore, in a preferred embodiment, these copolyimides exhibit recoverable semi-crystalline properties. These block copolyimides have melting points in the range of about 330 ° C to about 385 ° C to 395 ° C. The main melt processability parameters, including melting point and melt viscosity at the melting temperature, can be adjusted by appropriate selection of monomer, block length, molecular weight, and percentage of end capping. By using an appropriate molecular configuration in the copolyimide of the present invention, the window of the temperature difference between the melting point and the glass transition temperature can also be controlled.
[0035]
A major aspect of the present invention is that when the segmented (block) copolyimides of the present invention are prepared using sequenced polymerization, the melting point of the copolyimides and other desirable properties occur, while It is a surprising discovery that the crystallinity is maintained by cooling from a given copolyimide melt. It is highly desirable to obtain a semi-crystalline polyimide that retains strength above the glass transition temperature and then melts at higher temperatures for processing. When randomly placed in a chain of thermoplastic polyimide that can be crystallized, the crystallinity is destroyed and the amorphous comonomer or copolymer unit is unexpectedly crystallized when copolymerized in an ordered fashion. It has been found to retain the properties and to reduce the crystal melting. This sequence copolymerization is accomplished by adding monomers sequentially or by combining the amorphous polymer and the crystalline polymer separately and then combining to extend the chain. The novel compositions produced in the present invention can crystallize above the glass transition temperature, melt lower at a more practical temperature, lower for processing thin films, fibers and molded parts.
[0036]
The production of semi-crystalline thermoplastic polyimide generally requires molding and extrusion temperatures around 330-395 ° C. The upper temperature limit that can be achieved using current state-of-the-art high temperature equipment and prevents significant thermal decomposition of the polyimide is about 385-395 ° C. While random copolymerization can destroy the properties of crystals, sequence copolymerization more easily retains crystallinity and lowers the melting point of the crystals. As a result, lower and more practical manufacturing temperatures are achieved with the present invention.
[0037]
Semicrystalline all-aromatic homopolyimides often have melting points above the upper limit at which melt processability can be achieved. An example is BPDA / APB-134 homopolyimide, which has a melting point of about 400 ° C. (see Comparative Example 3), which is considered too high for practical melt processability.
[0038]
The main feature in the present invention is, surprisingly and unexpectedly, the copolymerization in an ordered manner to produce the segmented copolyimides of the present invention is a crystal from each melt of these copolyimides. While maintaining the properties, the melting point of these copolyimides is controlled and lowered, and thereby, the blocky copolyimide is given the characteristic of recoverable crystallinity.
[0039]
The segmented (block) copolyimide of the present invention is characterized by having a structure consisting of A // B segments or blocks, where A represents an amorphous or semicrystalline segment and B represents a semicrystalline segment. It is done. The A segment (block) is called a soft segment, and the B segment (block) is called a hard segment. A and B are both semi-soluble, provided that the A segment is sufficiently soluble at the processing temperature to form an A / B polyimide / poly (amic acid) copolymer in a suitable solvent (eg, DMAC, NMP). Although it may be crystalline, the A and B segments are always different in structure and are not identical. The A segment is preferably amorphous or very slightly to moderately semicrystalline and the B segment is semicrystalline. The main characteristics of the A segment are the solubility of the homopolyimide of the A segment in an organic solvent (such as DMAC) and the ability to lower the melting point of the block copolymer of the B segment without destroying recoverable crystallinity. Is included. The main characteristics of the B segment include having recoverable crystallinity and giving the block copolyimide a melting point of about 395 ° C. or less, preferably 385 ° C. or less.
[0040]
The present invention, in an embodiment, is a segmented polyimide / polyamic acid copolymer comprising a first imidized segment and a second amic acid segment.
[0041]
The first imidization segment is derived from the first amic acid segment as a precursor. First, the first acid dianhydride is selected from the group consisting of the first diamine and the acid anhydride and amine. It is obtained by reacting at a molecular ratio to obtain a first amic acid segment having the same terminal portion. Subsequently, the first amidic acid segment is imidized to form a first imidized segment. The first imidized segment is preferably terminally terminated.
[0042]
The first acid dianhydride and the first diamine (the second acid dianhydride and the second diamine) for forming the first imidized segment via the first amic acid segment as a precursor Independently) are combinations of ODPA and APB-133, BPDA and APB-133, PMDA and APB-133, 6FDA and APB-133, DSDA and APB-133, respectively. And a group consisting of a combination of 6FDA and APB-134. The first acid dianhydride and the first diamine are a combination of ODPA and APB-133, a combination of BPDA and APB-133, a combination of PMDA and APB-133, and 6FDA and APB-134, respectively. Preferably selected from the group consisting of combinations, more preferably selected from the group consisting of combinations of ODPA and APB-133, combinations of BPDA and APB-133, and combinations of PMDA and APB-133, respectively. Preferably, it is most preferably selected from the group consisting of a combination of ODPA and APB-133 and a combination of BPDA and APB-133, respectively. For certain applications requiring a material having a low dielectric constant, the first acid dianhydride and the first diamine are each a combination of 6FDA and APB-134, or a combination of 6FDA and APB-133. It is preferable that it is either.
[0043]
The second amic acid segment in the segmented polyimide / polyamic acid copolymer comprises a first imidized segment, (1) a second acid dianhydride and a second diamine or (2) a second amic acid segment and A first imidized segment obtained by reacting with one or more reactants that are any of linking monomers selected from the group consisting of acid dianhydrides and diamines, via an amide group having a carbon-nitrogen bond Forming a second amic acid segment linked to the.
[0044]
In the case of (1) above, an appropriate combination of a second acid dianhydride and a second diamine to form a second amic acid segment (first acid dianhydride and first diamine and Are independently selected from the group consisting of a combination of BPDA and APB-134, and a combination of BTDA and APB-134. The second acid dianhydride and the second diamine are each preferably a combination of BPDA and APB-134.
[0045]
In the case of (2) above, suitable second amic acid segments are BPDA / APB-134 and BTDA / APB-134. Examples 22-27 illustrate the case of (2) where the second amic acid segment is BPDA / APB-134, which contains 98% of stoichiometric amount of BPDA and therefore excess amino functionality Had. Thus, in these examples with excess amino functionality, the acid dianhydride is replaced with the second imidized segment rather than the diamine to increase the total stoichiometry of the segmented copolyimide to about 100%. Used as a linking monomer for linking to the amic acid segment. In Examples 22-27, BPDA was used as the linking monomer, but any other acid dianhydride can be used as the linking monomer in the present invention. Similarly, any diamine can be used as a linking monomer according to the present invention when the second amic acid has an excess of acid dianhydride functionality.
[0046]
When the second acid dianhydride and the second diamine are most preferably BPDA and APB-134, respectively, to form a first imidized segment via the first amic acid segment as a precursor Suitable combinations of the first acid dianhydride and the first diamine are ODPA and APB-133, BPDA and APB-133, PMDA and APB-133, 6FDA and It is selected from the group consisting of a combination with APB-133, a combination of DSDA and APB-133, and a combination of 6FDA and APB-134. The first acid dianhydride and the first diamine to form the first amidic acid segment and the first imidized segment are a combination of ODPA and APB-133, a combination of BPDA and APB-133, respectively. , And a combination of PMDA and APB-133. The first acid dianhydride and the first diamine to form the first amidic acid segment and the first imidized segment are a combination of ODPA and APB-133, and BPDA and APB-133, respectively. More preferably, it is selected from the group consisting of combinations. Most preferably, the first acid dianhydride and the first diamine to form the first amidic acid segment and the first imidized segment are a combination of ODPA and APB-133, respectively.
[0047]
The present invention, in another embodiment, is a segmented melt processable polyimide copolymer comprising a first imidized segment and a second imidized segment.
[0048]
The first imidization segment comprises a first acid dianhydride as a precursor having two identical terminal portions selected from the group consisting of a first diamine and an acid anhydride and an amine. It is obtained by reacting at a molecular ratio to obtain a segment. Subsequently, the first amidic acid segment is imidized to form a first imidized segment.
[0049]
The first acid dianhydride and the first diamine (the second acid dianhydride and the second diamine) for forming the first imidized segment via the first amic acid segment as a precursor Independently) are combinations of ODPA and APB-133, BPDA and APB-133, PMDA and APB-133, 6FDA and APB-133, DSDA and APB-133, respectively. And a group consisting of a combination of 6FDA and APB-134. The first acid dianhydride and the first diamine are a combination of ODPA and APB-133, a combination of BPDA and APB-133, a combination of PMDA and APB-133, and 6FDA and APB-134, respectively. Preferably selected from the group consisting of combinations, more preferably selected from the group consisting of combinations of ODPA and APB-133, combinations of BPDA and APB-133, and combinations of PMDA and APB-133, respectively. Preferably, it is most preferably selected from the group consisting of a combination of ODPA and APB-133 and a combination of BPDA and APB-133, respectively. For certain applications requiring a material having a low dielectric constant, the first acid dianhydride and the first diamine are each a combination of 6FDA and APB-134, or a combination of 6FDA and APB-133. It is preferable that it is either.
[0050]
The second imidized segment of the segmented copolyimide of the present invention comprises a first imidized segment, (1) a second acid dianhydride and a second diamine or (2) a second amic acid segment and Obtained by reacting with one or more reactants that are any of linking monomers selected from the group consisting of dianhydrides and diamines, to the first imidized segment via an amide group having a carbon-nitrogen bond. Forming a second amidic acid segment to be linked, followed by imidizing the second amic acid segment to form a second imidized segment, wherein the second acid diacid for forming the second segment is The combination of anhydride and second diamine (independent of the first acid dianhydride and first diamine) is the combination of BPDA and APB-134, respectively, and B It is selected from the group consisting of a combination of a DA and APB-134. The second acid dianhydride and the second diamine are each preferably a combination of BPDA and APB-134.
[0051]
When the second acid dianhydride and the second diamine are most preferably BPDA and APB-134, an appropriate combination of the first acid dianhydride and the first diamine to form the first segment The combinations are ODPA and APB-133, BPDA and APB-133, PMDA and APB-133, 6FDA and APB-133, DSDA and APB-133, respectively. And selected from the group consisting of a combination of 6FDA and APB-134. The first acid dianhydride and the first diamine to form the first segment are a combination of ODPA and APB-133, BPDA and APB-133, and PMDA and APB-133, respectively. It is preferably selected from the group consisting of combinations. The first acid dianhydride and the first diamine for forming the first segment are each selected from the group consisting of a combination of ODPA and APB-133, and a combination of BPDA and APB-133. Is more preferable. Most preferably, the first acid dianhydride and the first diamine to form the first segment are each a combination of ODPA and APB-133.
[0052]
The segmented melt processable polyimide copolymer of the present invention has a second segment (B segment) that is semi-crystalline. The second segment is preferably present in the copolymer in an amount greater than 60 weight percent. More preferably, the semi-crystalline segment is present in the copolymer in an amount ranging from 65 to 85 weight percent, and even more preferably the semi-crystalline segment is present in the copolymer in an amount ranging from 75 to 85 weight percent. .
[0053]
The segmented melt processable polyimide copolymer of the present invention has a first number average molecular weight (determined by gel permeation chromatography with a precursor segmented polyimide / polyamic acid copolymer) in the range of about 2,000 to about 20,000. The first segment consists of an imidized segment and the first segment has_nPreferably in the range of 4,000 to 10,000._nMore preferably, M in the range of 4,000 to 8,000_nMost preferably it has.
[0054]
Number average molecular weight of first imidized segment (M_n) Using the stoichiometric imbalance calculation (ie, using the Carothers formula) and the first acid dianhydride and the second acid required for a given molecular weight of the first imidization segment. By determining the amount of diamine of 1 that is out of the required stoichiometry, it can be set very strictly. Such a calculation is, for example,Principle of Polymerization, Third Edition, by George Odian, John Wiley and Sons, Inc. , New York (1991), p. This was done as described in many polymer textbooks such as 82-87.
[0055]
As illustrated in some of the examples, the number average molecular weight determined by titration analysis of the selected first imidization segment agrees very well with the molecular weight calculated based on the stoichiometric imbalance. It was.
[0056]
The present invention includes both segmented melt-processable semicrystalline polyimide copolymers and their precursor segmented polyimide / polyamic acid copolymers. Conversion of the amic acid segment to the corresponding imidized segment can be accomplished using thermal imidization and / or chemical imidization known to those skilled in the art (see section below).
[0057]
Many textbooks and other references (eg,Polyimides, Edited by D. Wilson, H.C. D. Stenzenberger, and P.M. M.M. Hergenroter, Blackkie, USA: see Chapman and Hall, New York, 1990), first by reaction in solution of one or more dianhydrides and one or more diamines to a poly (amidic acid). ) Occurs. Typical reaction temperatures are from room temperature to about 100 ° C. Subsequently, the poly (amide acid) is heated to an elevated temperature (eg, about 200-400 ° C.) and / or the poly (amide acid) is subjected to chemical imidization using a reagent such as a combination of triethylamine and acetic anhydride. The resulting poly (amic acid) can be converted to the corresponding polyimide (and water).
[0058]
[Table 1]

[0059]
[Table 2]

[0060]
[Table 3]

[0061]
[Table 4]

[0062]
Other
Poly (amic acid) = polyamic acid = first reaction product of dianhydride and diamine, polyimide precursor.
[0063]
【Example】
(Examples 1-21 and Comparative Examples 1-4)
General
All block copolyimides were synthesized using the general synthesis method disclosed in US Pat. No. 5,202,212. All acid dianhydrides and diamines used were of high purity polymer grade. Anhydrous N-methyl-2-pyrrolidinone (NMP) was used as the solvent. Aromatic hydrocarbon mixtures (Aromatic 150, Exxon) were used as azeotropic agents in the synthesis of these copolyimides. The same monomers and solvents were also used to synthesize random copolyimides for comparative examples. Prior to their use, all monomers were dried overnight at 40-50 ° C. for diamines and 160 ° C. for acid dianhydrides, then sealed in a bottle and stored in a desiccator. The GPC molecular weights reported below are relative values.
[0064]
Example 1
Synthesis of an uncapped ODPA / APB-133 (50) // BPDA / APB-134 (50) block copolyimide with a flexible block ("A" block) molecular weight of about 10,000 g / mole (as PI) I went there. The resulting sample was an uncapped block copolyimide.
[0065]
Assemble a dry 250 ml 4-neck round bottom flask equipped with a stirrer, nitrogen inlet, Dean-Stark trap / cooler, and thermometer (scaled up to about 250 ° C.) and heat gun just before the start of the reaction sequence Used to dry. 8.1290 g ODPA and NMP (30 ml) were added to the reaction flask and gentle stirring was started. APB-133 (7.2389 g) was weighed into a lidded container, NMP (30 ml) was added, and the mixture was stirred until all of APB-133 was dissolved. The resulting diamine solution was then added to the reaction flask with gentle stirring. The container was washed with NMP (10 ml), and the resulting wash was added to the flask. (The total volume (ml) of NMP added at the end of step # 3 was 70 ml and the mixture was about 17.5% solid.)
The resulting reaction mixture was stirred for 30 minutes.
[0066]
The Dean Stark trap was completely filled with Aromatic 150 fluid (Exxon). Aluminum foil was wrapped around the Dean Stark trap as a thermal insulator. Aromatic 150 liquid (8 ml) was added to the reaction mixture in the vessel and the resulting reaction mixture was heated at 180 ° C. for about 90 minutes. The reaction temperature was maintained at 180 ° C. for 3 hours, during which time the condensate dropped from the cooler at a constant rate, and water was collected in the Dean Stark trap.
[0067]
Increase the nitrogen flow through the reactor (about twice) and heat the relevant parts of the flask with a heat gun for about 5 minutes to remove any deposits adhering to the inside of the flask, then normalize the nitrogen flow rate. Returned. Heating was stopped until the reaction flask cooled to 45 ° C, then the reaction mixture was held at 60-70 ° C overnight. (In all subsequent examples relating to this example, at this point, heat was applied at a lower setting to keep the reaction mixture at 45 ° C. and the addition of BPDA / APB-134, described below, was performed at 45 ° C. on the same day. Performed after the temperature was established.)
[0068]
BPDA (7.4964 g) as well as 14 ml NMP (as wash) were added to the reaction mixture with gentle stirring. APB-134 (7.8708 g) was weighed into a stoppered container, NMP (25 ml) was added, and the resulting mixture was stirred until it became a solution. The solution was left plugged until dropped. The APB-134 solution was added dropwise over 30 minutes to the stirring reaction mixture using a dropping funnel. At the end of the addition, the stoppered container was washed with NMP (10 ml) and the washings were added to the reaction mixture. (The approximate volume of the reaction mixture at this point was 150 ml. A total of 119 ml of NMP was added.) After completion of the addition, the reaction mixture was stirred at 45 ° C. for 1 hour and then at room temperature for another overnight. . The resulting intermediate product, polyimide / polyamic acid copolymer, was collected and stored in a dry stoppered container.
[0069]
GPC molecular weight measurements on this sample as an intermediate polyimide / polyamic acid gave the following results: M_w= 352K and M_n= 162K.
[0070]
The intermediate polyimide / polyamic acid solution sample described above is spin coated onto a wafer, pre-baked at 135 ° C. for 30 minutes in air, and baked at 350 ° C. for 60 minutes in nitrogen to corrode the wafer support and remove the thin film. Conversion to a polyimide film sample by washing with water and then drying yielded a final polyimide film sample suitable for characterization tests. This polyimide thin film showed a melting point of 367 ° C. in the first DSC scan.
[0071]
(Note: In Example 1, the initial reaction mixture after addition of APB-134 gelled and showed a rubbery consistency. This was diluted from about 20% to about 15% by weight solids and spin coated. Is a solution that works well.)
(Example 2)
Synthesis of ODPA / APB-133 (40) // BPDA / APB-134 (60) block copolyimide (uncapped) with an “A” block size of 10K in a manner similar to that described in Example 1. The monomer amount was adjusted as follows: ODPA 8.1277 g; APB-133 7.2378 g; BPDA 11.3505 g; and APB-134 11.6993 g. The initial reaction mixture (after adding BPDA and APB-134 and heating to 45 ° C.) was highly viscous. This was diluted with 20 ml of anhydrous NMP and a moderately viscous reaction mixture was spin coated successfully to produce a polyimide film sample for characterization (similar to Example 1). This polyimide thin film had a melting point of 375 ° C. in the first DSC scan.
[0072]
GPC molecular weight analysis of this sample as an intermediate polyimide / polyamic acid gave the following results: M_w= 393K and M_n= 183K.
[0073]
(Example 3)
The synthesis of ODPA / APB-133 (50) // BTDA / APB-134 (50) block copolyimide (uncapped) with an “A” block size of 5K was synthesized in a manner similar to that described in Example 1. The amount of monomer was adjusted as follows: ODPA 8.3460 g; APB-133 7.02.010 g; BTDA 7.6144 g; and APB-134 7.7540 g. The reaction mixture (after adding BTDA and APB-134 and heated to 45 ° C.) was stirred over the weekend at room temperature and directly spin coated as a moderately viscous solution (similar to Example 1). ) Polyimide thin film sample for characterization. This polyimide thin film showed a low melting point of 358 ° C. and a high melting point of 391 ° C. in the first DSC scan.
[0074]
GPC molecular weight analysis of this sample as an intermediate polyimide / polyamic acid gave the following results: M_w= 98K and M_n= 50K.
[0075]
(Comparative Example 1)
Synthesis of ODPA / APB-133 (50) // PMDA / APB-133 (50) block copolyimide (uncapped) with an “A” block size of 5K, in a manner similar to that described in Example 1. The amount of monomer was adjusted as follows: OD462 8.3462 g; APB-133 (as first diamine) 7.0201 g; PMDA 5.8130 g; and APB-133 (second 8.6354 g) as diamine. The polyimide / polyamic acid reaction mixture (after the addition of the second diamine and the second acid dianhydride and heating to 45 ° C.) is stirred in the usual manner overnight to give a moderately viscous solution. Direct spin coating (similar to Example 1) yielded polyimide thin film samples for characterization. This polyimide thin film showed no melting point in the first DSC scan.
[0076]
GPC molecular weight analysis of this sample as an intermediate polyimide / polyamic acid gave the following results: M_w= 64.8K and M_n= 29.7K.
[0077]
(Comparative Example 2)
Synthesis of 6FDA / APB-133 (50) // BPDA / 4,4'-ODA (50) block copolyimide (uncapped) with “A” block size of 5K is similar to that described in Example 1 In this manner, the amount of monomer was adjusted as follows: 9.5367 g of 6FDA; 5.8308 g of APB-133 (as the first diamine); 8.5340 g of BPDA; and 4,4 ′ -6.1188 g of ODA (as the second diamine). The polyimide / polyamic acid reaction mixture (after the addition of the second diamine and the second acid dianhydride and heating to 45 ° C.) is stirred in the usual manner overnight to give a moderately viscous solution. A polyimide thin film sample for characterization was obtained by direct spin coating. This polyimide thin film showed no melting point in the first DSC scan.
[0078]
GPC molecular weight analysis of this sample as an intermediate polyimide / polyamic acid gave the following results: M_w= 118K and M_n= 33.9K.
[0079]
(Comparative Example 3)
The synthesis of ODPA / APB-133 (50) // DSDA / APB-134 (50) block copolyimide (uncapped) with an “A” block size of 5K was synthesized in a manner similar to that described in Example 1. The monomer amount was adjusted as follows: ODPA 8.3450 g; APB-133 (as the first diamine) 7.0224 g; DSDA 7.9993 g; and APB-134 (second 7.3693 g) as diamine. The polyimide / polyamic acid reaction mixture (after adding the second diamine and the second acid dianhydride and heating to 45 ° C.) is stirred overnight in the usual manner to give a moderately viscous solution. Was directly spin coated to obtain a polyimide thin film sample for characterization. This polyimide thin film showed no melting point in the first DSC scan.
[0080]
GPC molecular weight analysis of this sample as an intermediate polyimide / polyamic acid gave the following results: M_w= 114K and M_n= 59.1K.
[0081]
(Comparative Example 4)
Synthesis of ODPA / APB-133 (50) // BPDA / PPD (50) block copolyimide (uncapped) with an “A” block size of 5K in a manner similar to that described in Example 1 Were adjusted as follows: ODPA 8.3455 g; APB-133 (as the first diamine) 7.0210 g; BPDA 11.0088 g; and PPD (as the second diamine) 4.3589 g. The polyimide / polyamic acid reaction mixture (after adding the second diamine and the second acid dianhydride and heating to 45 ° C.) is stirred overnight in the usual manner to give a moderately viscous solution. Was directly spin coated to obtain a polyimide thin film sample for characterization. This polyimide thin film showed no melting point in the first DSC scan.
[0082]
GPC molecular weight analysis of this sample as an intermediate polyimide / polyamic acid gave the following results: M_w= 238K and M_n= 118K.
[0083]
Example 4
Using differential scanning calorimetry (DSC) (as shown in the previous examples and comparative examples), some of the three block copolyimide samples shown in the previous examples 1-3 and in the above comparative examples 1-4 The thermal behavior of about 15-20 other block copolyimides that showed Each sample was subjected to a single DSC scan from room temperature to 500 ° C. at a scan rate of 20 ° C./min. As described in the individual examples, the block copolyimide samples of Examples 1-3 each exhibit DSC melting point behavior (ie, exhibit a characteristic melting point curve in the DSC trace), each of which is semicrystalline. It was found to have the following properties. In contrast, the other 15 to 20 sample groups (including the samples of Comparative Examples 1 to 4) do not exhibit DSC melting point behavior, and it is clear that they basically have an amorphous nature. there were.
[0084]
(Example 5)
Synthesis of a capped ODPA / APB-133 (50) // BPDA / APB-134 (50) block copolyimide with a flexible block ("A" block) molecular weight of about 10000 g / mol (as PI) is as follows: Performed as described.
[0085]
All monomers were dried overnight at 40-50 ° C. for diamines and 160 ° C. for dianhydrides, then sealed in a bottle and stored in a desiccator. Assemble a dry 250 ml 4-neck round bottom flask equipped with a stirrer, nitrogen inlet, Dean-Stark trap / cooler, and thermometer (scaled up to about 250 ° C.) and heat gun just before the start of the reaction sequence Used to dry. To the reaction flask was added 8.1288 g ODPA and NMP (30 ml) and gentle stirring was started. APB-133 (7.2371 g) was weighed into a lidded container, NMP (35 ml) was added and the mixture was stirred until all of APB-133 was dissolved. The resulting diamine solution was then added to the reaction flask with gentle stirring. The container was washed with NMP (5 ml), and the resulting wash was added to the flask. (The total volume (ml) of NMP added at the end of the above step was 70 ml and the mixture was about 17.5% solid.) The resulting reaction mixture was stirred for 30 minutes.
[0086]
The Dean Stark trap was completely filled with Aromatic 150 fluid (Exxon). Aluminum foil was wrapped around the Dean Stark trap as a thermal insulator. Aromatic 150 solution (8 ml) was added to the reaction mixture in the vessel and the resulting reaction mixture was heated to 180 ° C. over about 90 minutes. The reaction temperature was maintained at 180 ° C. for 3 hours, during which time condensate dropped from the cooler at a constant rate and water was collected in the Dean-Stark trap. Increase the nitrogen stream passing through the reactor (about twice), heat the relevant part of the flask with a heat gun for about 5 minutes to remove the condensate adhering to the inside of the flask, and then adjust the nitrogen stream rate to normal Returned to initial speed. Heating was stopped until the reaction flask cooled to 45 ° C, then heat was applied at a lower setting to keep the reaction mixture at 45 ° C. BPDA (7.2710 g) as well as 10 ml NMP (as wash) were added to the reaction mixture with gentle stirring and stirring was continued for 10 minutes. Phthalic anhydride (PA, 0.2264 g) was then added to the reaction mixture using 4 ml of NMP as a wash. APB-134 (7.8710 g) was weighed into a stoppered container, NMP (30 ml) was added, and the resulting mixture was stirred until it became a solution. The solution was left plugged until dropped. The aforementioned APB-134 solution was added dropwise over 30 minutes to the stirring reaction mixture using a dropping funnel. At the end of the addition, the stoppered container was washed with NMP (10 ml) and the wash was added to the reaction mixture (the approximate volume of the reaction mixture at this point was 150 ml. A total of 119 ml of NMP was added. ). After completion of the addition, the reaction mixture was stirred at 45 ° C. for 1 hour and then further stirred at room temperature overnight. The resulting intermediate product, a polyimide / polyamic acid copolymer solution containing about 20% by weight solids, was collected and stored in a dry stoppered container. This polyimide / polyamic acid reaction mixture had a moderate viscosity. This was chemically imidized using the method shown below to obtain a block copolyimide polyimide powder sample for DSC analysis (to provide the properties described above).
[0087]
The chemical imidization method used is shown below. A 100 ml reaction vessel (flask + head) for chemical imidation equipped with nitrogen purging (in / out) and stirrer was assembled. (Normally 2-4 of these were performed simultaneously.) The block PI / PAA copolyimide sample (50.0 g) described above was added to the reaction vessel. Two clean and dry 10 ml measuring pipettes (with a 0.02 ml scale) were used, one weighed acetic anhydride and the other weighed triethylamine. The specified amount (below) of acetic anhydride (AA) was added to the reaction mixture while moderately stirring the copolyimide sample. The reaction mixture became cloudy. Stirring was continued at room temperature until a clear and homogeneous reaction mixture was obtained. While continuing to stir, the specified amount of triethylamine (Et₃N) was added to the reaction mixture. (A precipitate formed immediately after the addition of triethylamine.) Stirring was continued for about 6 hours (or overnight) at room temperature, during which time the resulting mass was periodically broken up.
[0088]
The reaction mixture was poured into methanol in a powered Waring blender causing polyimide precipitation. The resulting precipitate was collected by vacuum filtration using a Buchner funnel with filter paper. The resulting solid was dried over two consecutive nights. On the first night, the sample was dried at 100 ° C. in a vacuum dryer. On the second night, final drying was performed in a vacuum dryer set at about 200-210 ° C. After final drying, any large lumps were broken down to obtain a reasonably homogeneous powder. The resulting powder sample was used for analysis and characterization.
[0089]
The amount of the chemical imidizing reagent used in Example 5 is shown below.
[0090]
[Table 5]

[0091]
This polyimide sample showed a melting point of 374 ° C. and a heat of fusion of 11.4 J / g in the first DSC scan. There was no melting point during the second and third DSC scans, and therefore no recoverable semi-crystalline properties.
[0092]
(Examples 6 to 13)
The synthesis of the other eight capped block copolyimides listed below was adjusted in the same manner as in Example 5 above, except for the amount of chemical imidization reagent used and the amount of monomer as follows: I went.
[0093]
[Table 6]

[0094]
[Table 7]

[0095]
[Table 8]

[0096]
(Example 14)
Each of the powder polyimide samples from Examples 5-13 was subjected to DSC analysis to determine the melting point, glass transition, and crystallization characteristics of the samples in relation to their structural characteristics. The first DSC analysis up to 500 ° C. is based on the appropriate upper temperature limit (T_ul) Went to determine. This T_ulWas selected to be above the temperature of all significant transitions (melting, glass transition, etc.), but below the temperature at which obvious decomposition occurs at higher temperatures. In each case, the original sample was discarded and a new sample was used instead for repeated scan DSC.
[0097]
A repeated scan DSC was then performed in the following manner:
1) From room temperature to T_ulFirst heating scan at 10 ° C / min until.
2) T_ulLow-speed cooling scan at 10 ° C / min from room temperature to room temperature.
3) From room temperature to T_ul2nd heating scan at 10 ° C / min until.
4) T_ulUncontrolled quench scan from to room temperature.
5) A third heating scan from room temperature to 500 ° C. at 10 ° C./min.
[0098]
All the samples showed the first DSC melting point behavior during the first DSC scan (first heating described below), which revealed that these copolyimides were semi-crystalline. Only block compositions with an A block to B block ratio of 30:70 or 20:80 were found to exhibit the desired recoverable semi-crystallinity, and these samples exhibited DSC melting behavior in three scans (1 (Second heating, second heating, and third heating) all showing that the sample can be crystallized from the melt.
[0099]
Specific properties measured for these copolyimides are shown below.
[0100]
[Table 9]

[0101]
The copolyimides of Examples 10-13 showed significant crystallization peaks during the first cooling scan and / or the second heating scan. Peaks were seen in the range of 286-318 ° C and heats of fusion in the range of 13-18.1 Joules / gram.
[0102]
(Example 15)
Selected block and random copolyimide samples were characterized for melt viscosity using a capillary rheometer. Measurements are 100, 200, 500, 1000, and 2000 seconds^-1Of 5 different shear rates. Usually two measurements are taken at one shear rate, which is usually 1000 seconds^-1Met. The results obtained with representative blocks and random copolyimides are shown below.
[0103]
[Table 10]

[0104]
From these melt viscosity measurements, an apparent viscosity of 100 Pa. At a shear rate of 500 / sec. M for S_wAn important result was shown that the ODPA / APB-133 // BPDA / APB-134 block copolyimide of about 60K has a sufficiently low melt viscosity to be melt processable without any additives.
[0105]
(Comparative Example 5)
Synthesis and characterization of DSC melting behavior and melt viscosity of ODPA (20) / BPDA (80) / APB-133 (20) / APB-134 (80) random copolyimide with 6 mol% phthalic anhydride end cap Was performed for comparison with the corresponding block copolyimide described above. The random tetrapolyimide was synthesized as follows.
[0106]
All monomers were dried overnight at 40-50 ° C. for diamines and 160 ° C. for acid dianhydrides, then sealed in bottles, taped and stored in a desiccator. Assemble a dry 250 ml 4-neck round bottom flask equipped with a stirrer, nitrogen inlet, Dean-Stark trap / cooler, and thermometer (scaled up to about 250 ° C.) and heat gun just before the start of the reaction sequence Used to dry. NMP (60 ml) was added to the reaction flask and gentle stirring was started. ODPA (8.206 g) and BPDA (29.6316 g) were added as powders to the stirring reaction mixture as a slurry, and 10 mL NMP was used as a wash to transfer all acid dianhydride powder samples to the reaction flask. A solution of APB-133 (7.1654 g) and APB-134 (30.9160 g) in NMP (170 ml) was prepared and added to the dropping funnel prepared for dropping. Phthalic anhydride (0.9227 g) and NMP (10 ml as a wash) were added to the stirring reaction mixture, followed immediately by the next step. The above diamine solution was added to the stirring reaction mixture over 10-20 minutes. Additional NMP (5 ml) was added as a wash. (A total of 298 ml of NMP was added. The approximate reaction mixture volume was 374 ml.) The resulting polyamic acid mixture was stirred at room temperature overnight. The following molecular weight data was obtained by GPC analysis of the polyamic acid mixture: M_n= 94.8K and M_w= 180K.
[0107]
A sample of the resulting intermediate polyimide / polyamic acid mixture was subjected to the aforementioned chemical imidation using 6.35 ml of acetic anhydride and 9.39 ml of triethylamine to obtain a solid powder sample of this random copolyimide. This random copolyimide was found by DSC analysis to have a melting point of 326 ° C. and a heat of fusion of 11.9 J / g in the first DSC scan. The melting point DSC curve was very wide (compared to the corresponding block copolyimide). No melting behavior was observed in the second and third scans, demonstrating that this random copolyimide does not exhibit recoverable semi-crystalline properties. As evidenced by the melting point behavior in the first scan, it has the initial semi-crystallinity.
[0108]
(Comparative Example 6)
Preparation of polyimide with BPDA / APB-134 / PA 98/100/4 (8% stoichiometric acid dianhydride)
BPDA (14.414 g, 0.04899 mol) and DMAC (175 ml) were mixed to form a slurry (BPDA has very low solubility in DMAC). PA (0.296 g) was added to the slurry with stirring, and then APB-134 (14.617 g, 0.05 mol) was added to the stirring slurry. The resulting mixture was stirred overnight at room temperature and confirmed to have the following characteristics as a polyamic acid solution of BPDA / APB-134 / PA. Inherent viscosity = η_inh= 0.86 deciliter / gram (dl / g).
[0109]
The above polyamic acid solution was chemically imidized using the following method to obtain a BPDA / APB-134 homopolyimide endcapped with PA. TEA (0.72 ml) and AA (1.08 ml) were added to the above polyamic acid solution with stirring, and the resulting mixture was stirred at 30 ° C. for 18 hours, after about 1 hour at 30 ° C. Was observed. The resulting polyimide was isolated using a ratio of about 10 g polymer solution to 500 ml methanol in methanol in a Waring blender. After filtration, an additional Waring blender treatment with 500 ml of methanol was performed followed by drying to constant weight at 200 ° C. under nitrogen and vacuum.
[0110]
The resulting polyimide was characterized by DSC. The DSC test was performed with three heating scans from room temperature to a minimum of 410 ° C. followed by a cooling scan between each heating scan. For each scan, the glass transition temperature (T_g), Crystallization temperature (T_c) And melting point (T_m) Was measured. The crystallization temperature was the DSC output peak of the crystallization transition, and the melting point was the DSC output peak of the melting transition. For this BPDA / RODA homopolyimide,_mThe measured value was 403 ° C. in the second heating and 404 ° C. in the first heating. T_gThe measured values are 200 ° C. (second heating) and 218 ° C. (third heating)._c(Second heating) The measured value was 222 ° C. This end-capped homopolyimide exhibits a semicrystalline and recoverable semicrystalline character (proven by the melting point observed in the second and third thermal scans), but its melting point above 400 ° C is melt processed. Too expensive for sex. This is therefore a comparative example.
[0111]
(Examples 16 to 19)
General
This example illustrates that other selected block copolyimides are semi-crystalline and exhibit melting points below 390 ° C. as well as recoverable DSC melting point behavior. From the approximately 25 other capped block copolyimide composition groups having different monomer and A: B block ratios initially synthesized and tested, the following four were semicrystalline by DSC (Differential Scanning Calorimetry) analysis: Polyimide has been found to exhibit the desired recoverable DSC melting point behavior within the desired melting point range. Recoverable DSC melting point behavior is an important indicator that a polymer sample can be recrystallized from the melt as desired. Each of these block copolyimides is obtained as a solution of a polyimide / polyamic acid block copolymer using the synthesis method described in US Pat. No. 5,202,212, and end capping is usually up to 97% stoichiometric with phthalic anhydride. there were. The obtained PI / PAA solution is subjected to chemical imidation, and processed and dried as a polyimide powder sample. This is subjected to DSC analysis, and the thermal characteristics (T_g, T_m, And T_cEtc.).
[0112]
[Table 1]

^aThe synthesis of the above four block copolyimides is shown in Examples 16-19.
[0113]
(Example 16)
The synthesis of a capped BPDA / APB-133 (20) // BPDA / APB-134 (80) block copolyimide with a flexible block ("A" block) molecular weight of 7500 g / mol (as PI) is described below. It carried out as follows. The sample was 97 mol% of stoichiometry in acid dianhydride and endcapped with 6 mol% phthalic anhydride. In order to synthesize, the following steps were performed.
[0114]
All monomers were dried overnight at 40-50 ° C. for diamines and 160 ° C. for dianhydrides, then sealed in a bottle and stored in a desiccator. Assemble a dry 500 ml 4-neck round bottom flask equipped with a stirrer, nitrogen inlet, Dean-Stark trap / cooler, and thermometer (scaled to about 250 ° C.) and heat gun just before the start of the reaction sequence Used to dry. The apparatus was adjusted so that a thermometer was used with a first reaction volume of about 85 ml in a 500 ml flask. BPDA (7.9896 g) and NMP (30 ml) were added to the reaction flask and gentle stirring was started.
[0115]
APB-133 (7.37711 g) was weighed into a covered container, NMP (35 ml) was added, and the mixture was stirred until all of APB-133 was dissolved. The resulting diamine solution was then added to the reaction flask with gentle stirring. The container was washed with NMP (5 ml), and the resulting wash was added to the flask. (The total volume (ml) of NMP added at the end of the above step was 70 ml and the mixture was about 17.5% solid.) The resulting reaction mixture was stirred for 30 minutes.
[0116]
The Dean Stark trap was completely filled with Aromatic 150 fluid (Exxon). Aluminum foil was wrapped around the Dean Stark trap as a thermal insulator. Aromatic 150 solution (8 ml) was added to the reaction mixture in the vessel and the resulting reaction mixture was heated to 180 ° C. over about 90 minutes. The reaction temperature was maintained at 180 ° C. for 3 hours, during which time the condensate dropped from the cooler at a constant rate, and water was collected in the Dean Stark trap. Increase the nitrogen stream passing through the reactor (about twice), heat the relevant part of the flask with a heat gun for about 5 minutes to remove the condensate adhering to the inside of the flask, and then adjust the nitrogen stream rate to normal Returned to initial speed. Heating was stopped until the reaction flask cooled to 45 ° C, then heat was applied at a lower setting to keep the reaction mixture at 45 ° C. BPDA (29.6327 g) as well as 110 ml NMP (as a wash) were added to the reaction mixture with gentle stirring and stirring was continued for 10 minutes. Phthalic anhydride (PA, 0.9227 g) was then added to the reaction mixture using 10 ml of NMP as a wash. APB-134 (30.9154 g) was weighed into a stoppered container, NMP (100 ml) was added, and the resulting mixture was stirred until it became a solution. The solution was left plugged until dropped. The aforementioned APB-134 solution was added dropwise to the stirring reaction mixture using a dropping funnel over 5 to 10 minutes. At the end of the addition, the stoppered container was washed with NMP (8 ml) and the washings were added to the reaction mixture. (The approximate volume of the reaction mixture at this point was 374 ml. A total of 298 ml of NMP was added.) After completion of the addition, the reaction mixture was stirred at 45 ° C. for 1 hour and then at room temperature for another overnight. . The resulting intermediate product, a polyimide / polyamic acid copolymer solution containing about 20% by weight solids, was collected and stored in a dry stoppered container. This polyimide / polyamic acid reaction mixture had a moderate viscosity. This was chemically imidized using the method shown below to obtain a block copolyimide polyimide powder sample for DSC analysis (to provide the properties described above).
[0117]
The chemical imidization method used is shown below. A 100 ml reaction vessel (flask + head) for chemical imidation equipped with nitrogen purging (in / out) and stirrer was assembled. (Normally 2-4 of these were performed simultaneously.) The block PI / PAA copolyimide sample (50.0 g) described above was added to the reaction vessel. Two clean and dry 10 ml measuring pipettes (with a 0.02 ml scale) were used, one weighed acetic anhydride and the other weighed triethylamine. The specified amount (below) of acetic anhydride (AA) was added to the reaction mixture while moderately stirring the copolyimide sample. The reaction mixture became cloudy. Stirring was continued at room temperature until a clear and homogeneous reaction mixture was obtained. While continuing to stir, the specified amount of triethylamine (Et₃N) was added to the reaction mixture. (A precipitate formed immediately after the addition of triethylamine.) Stirring was continued for about 6 hours (or overnight) at room temperature, during which time the resulting mass was periodically broken up.
[0118]
The reaction mixture was poured into methanol in a powered Waring blender causing precipitation. The resulting precipitate was collected by vacuum filtration using a Buchner funnel with filter paper. The resulting solid was dried continuously for 2 nights. On the first night, the sample was dried at 100 ° C. in a vacuum dryer. On the second night, final drying was performed in a vacuum dryer set at about 200-210 ° C. After final drying, any large lumps were broken down to obtain a reasonably homogeneous powder. The resulting powder sample was used for analysis and characterization.
[0119]
The amount of chemical imidization reagent used in Example 16 is shown below.
[0120]
[Table 12]

[0121]
(Examples 17 to 19)
The synthesis of each of the other three capped block copolyimides in this series of examples (above) was carried out in the same manner as in Example 16 above, with the amount of monomers and the chemicals used in the synthesis of the block PI / PAA. Only the amount of the imidizing reagent was adjusted as follows.
[0122]
[Table 13]

[0123]
[Table 14]

[0124]
(Example 20)
Each of the powder polyimide samples from Examples 16-19 was subjected to DSC analysis to determine the melting point, glass transition, and crystallization characteristics of the samples in relation to their structural characteristics. The first DSC analysis involves the appropriate upper temperature limit of the sample (T_ul) Went to determine. This T_ulWas selected to be above the temperature of all significant transitions (melting, glass transition, etc.), but below the temperature at which obvious decomposition occurs at higher temperatures. In each case, the original sample was discarded and a new sample was used instead for repeated scan DSC.
[0125]
A repeated scan DSC was then performed in the following manner:
1) From room temperature to T_ulFirst heating scan at 10 ° C / min until.
2) T_ulLow-speed cooling scan at 10 ° C / min from room temperature to room temperature.
3) From room temperature to T_ul2nd heating scan at 10 ° C / min until.
4) T_ulRapid cooling scan to room temperature.
5) A third heating scan from room temperature to 500 ° C. at 10 ° C./min.
[0126]
The DSC test results for this series of block copolyimides are summarized below. Only a few of the many block compositions tested (about 25) were found to be semi-crystalline by DSC analysis, and even fewer showed the desired recoverable DSC melting point behavior. Furthermore, these block copolyimides have been shown to exhibit fast recrystallization kinetics, which can be a great advantage. These block copolyimides have a glass transition temperature (T_g) Is somewhat higher than the ODPA / APB-133 // BPDA / APB-134 block copolyimide sample described in the previous example or the random copolyimide described in the comparative example.
[0127]
Specific properties measured for these copolyimides are shown below.
[0128]
[Table 15]

[0129]
Each of the aforementioned capped block copolyimide samples was found to exhibit recoverable DSC melting behavior, most notably at about 380 ° C. (measured in heat of fusion / polymer weight (g)). This behavior indicates that each of these copolyimides is semi-crystalline when first obtained from solution and further crystallizes from the melt as desired for melt processable PI. (In contrast to these block copolyimides containing BPDA / APB-134 as the “B” block, the corresponding BPDA / APB-134 homopolyimide has a melting point above 400 ° C.—see Comparative Example 6).
[0130]
(Comparative Example 7)
Synthesis and DSC melting behavior of BPDA / APB-133 (20) / APB-134 (80) random copolyimide with 6 mol% phthalic anhydride endcap (97% of stoichiometric acid dianhydride) and Characterization for melt viscosity was performed for comparison with the corresponding block copolyimide described above. The random tetrapolyimide was synthesized as follows.
[0131]
All monomers were dried overnight at 40-50 ° C for diamines and 160 ° C for acid dianhydrides, then sealed in bottles, taped and stored in a desiccator. Assemble a dry 250 ml 4-neck round bottom flask equipped with a stirrer, nitrogen inlet, Dean-Stark trap / cooler, and thermometer (scaled up to about 250 ° C.) and heat gun just before the start of the reaction sequence Used to dry. NMP (100 ml) was added to the reaction flask and gentle stirring was started. BPDA (18.8119 g) was added as a powder to the stirring reaction mixture as a slurry, and 10 ml NMP was used as a wash to transfer all acid dianhydride powder samples to the reaction flask. A solution of APB-133 (3.6878 g) and APB-134 (15.4582 g) in NMP (60 ml) was prepared and added to the dropping funnel prepared for dropping. Phthalic anhydride (0.4614 g) and NMP (4 ml as a washing solution) were added to the stirring reaction mixture, followed immediately by the next step. The above diamine solution was added to the stirring reaction mixture over 10-20 minutes. Additional NMP (8 ml) was added as a wash. (A total of 149 ml of NMP was added. The approximate reaction mixture volume was 187 ml.)
[0132]
The resulting polyamic acid mixture was stirred at room temperature overnight. The following molecular weight data was obtained by GPC analysis of the polyamic acid mixture: M_n= 49.2K and M_w= 142K.
[0133]
A sample of the resulting intermediate polyimide / polyamic acid mixture was subjected to the aforementioned chemical imidation using 5.19 ml of acetic anhydride and 7.67 ml of triethylamine to obtain a solid powder sample of this random copolyimide. This random copolyimide was found by DSC analysis to have a melting point of 352 ° C. and a heat of fusion of 21.1 J / g in the first DSC scan. The melting point DSC curve was very wide (compared to the corresponding block copolyimide). In the second DSC heat scan, the melting point was 348 ° C., but the heat of fusion dropped dramatically to 3.0 J / g. In the third heating scan, no melting point behavior was observed. Thus, this copolyimide was characterized as semi-crystalline (proven by some melting behavior in the first and second scans) but does not exhibit significant recoverable semi-crystallinity. .
[0134]
(Examples 22 to 27)
These examples illustrate block copolyimides with recoverable crystallinity synthesized using an alternative method to achieve the following sequence polymerization. Six block copolyimides were prepared using acid dianhydride and diamine components including ODPA, BPDA, APB-133, and APB-134. No phthalic anhydride endcapping was used.
[0135]
A sequence polymerization method was used, which consisted of first preparing a series of ODPA / APB-133 soluble oligomeric polyimides by thermal imidization of the corresponding polyamic acids. Each of these materials in excess of amino functionality was separately mixed with a certain amount of polyamic acid of BPDA / APB-134 containing 98% stoichiometric amount of BPDA. The copolymer was then formed by adding the necessary amount of BPDA to consume all excess amino groups. The resulting copolymer was composed of ODPA / APB-133 imidized chain segments linked to BPDA / APB-134 unconverted amic acid chain segments.
[0136]
The partially imidized block copolymer described above is completely converted to a fully imidized block copolyimide using acetic anhydride and triethylamine, and each copolyimide is simply converted into a powdered polyimide resin with excess acetone in a blender. Released. The product was dried to constant weight at 200 ° C. under nitrogen and reduced pressure before further characterization and proof of utility. Details are shown below.
[0137]
Preparation of ODPA / APB-133-Part A
In a nitrogen filled glove box, the following amount of ODPA was added to the APB-133 solution with stirring. The reaction mixture was stirred for 3 hours, then 40 ml of reagent grade xylene was first added and after stirring at reflux, the imidized water was collected in a Dean-Stark trap. After stripping off xylene, the resulting oligomeric imide was soluble.
[0138]
[Table 16]

[0139]
Preparation of BPDA / APB-134-Part B
For each oligomeric imide preparation (Part A), the following polyamic acid was produced. A constant amount (23.287 g) of APB-134 was dissolved in 277 ml of anhydrous NMP in a nitrogen filled glove box. To this solution 23.066 grams of BPDA was added over 20 minutes with stirring. The mixture was stirred overnight to give a clear polyamic acid.
[0140]
Preparation of block copolyamic acid / imide-Part C
Each polyimide oligomer sample from part A was combined with one of the polyamic acid samples from part B. As shown below, the required amount of BPDA was added with NMP and the resulting reaction mixture was stirred for 4 hours to give 6 copolyamic acids / imides (samples from Examples 22-27).
[0141]
[Table 17]

[0142]
Preparation of all imidized block copolyimides-Part D
Each copolyamic acid / imide of Part C is mixed with 100 grams each of 13 ml of triethylamine and 9 ml of acetic anhydride, and then the reaction mixture is left under nitrogen for 24 hours to form an all imidized block (array) copolymer. Chemically converted to polyimide. The product was precipitated in acetone in a blender. After filtration, the product was washed twice with acetone by moderate filtration in a blender. In each case, the resin was dried in a vacuum dryer under nitrogen at 200 ° C. to a constant weight.
[0143]
Each sample was analyzed by DSC. DSC analysis was performed using a Mettler TA 3000 system and a large aluminum pan. The polymer was kept dry under nitrogen and weighed just prior to analysis. The sample weight was in the range of 35 to 50 mg, preferably 40 mg, and weighed to the nearest 1/10 milligram. After capping the sample with a Mettler device and making a small hole in the pan cap, DSC analysis was performed to 400 ° C. at a rate of 10 ° C./min. The dish and contents were immediately cooled in dry ice. The sample was then heated at the same rate to 400 ° C. under nitrogen and quenched again. Where a third trial was desired, the same heating rate and maximum temperature were applied.
[0144]
[Table 18]

[0145]
As the results clearly show, these block (array) copolyimides have unique recoverable crystallinity retention.
[0146]
【The invention's effect】
As described above, according to the present invention, it is possible to provide a polyimide copolymer having characteristics such as high thermal stability, melt processability, and recoverable crystallinity at the same time. Copolymers according to the present invention have a suitably low melt viscosity to be melt processable, or have a suitably low melt viscosity to be melt processable by adding certain additives. It is possible to Also, adjustment of the melting point and glass transition temperature of the copolymer can be achieved by changing its molecular composition. Therefore, the polyimide copolymer of the present invention can be processed in a melt state to form an article, and the processed article has a predetermined shape such as an extruded product, a fiber, a film, and a molded product. In many cases, the copolymer of the present invention can also be produced via melt polymerization, thus eliminating the need for redundant and expensive solvent recycling in the production process.

Claims (9)

A segmented polyimide / polyamic acid copolymer comprising a first imidized segment and a second amic acid segment having a number average molecular weight in the range of 2,000 to 20,000, wherein the segment of the second amic acid segment The proportion of the second imidized segment in the copolymer when the second amidic acid segment is imidized to form the second imidized segment is 60% by weight or more. A proportion of the copolymer in the following steps:
(A) preparing a first amic acid segment,
A first amic acid segment is a precursor of the first imidized segment and has a first amic acid segment having two identical terminal portions selected from the group consisting of an acid anhydride and an amine A reaction product obtained by reacting the first acid dianhydride with the first diamine at a molecular ratio of
The combination of the first acid dianhydride and the first diamine to form the first amic acid segment is 4,4'-oxydiphthalic anhydride (ODPA) and 1,3-bis (3- In combination with (aminophenoxy) benzene (APB-133), (3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,3-bis (3-aminophenoxy) benzene (APB- 133), a combination of pyromellitic dianhydride (PMDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), (2,2'-bis- (3,4-di) Carboxyphenyl) hexafluoropropane dianhydride (6FDA) in combination with 1,3-bis (3-aminophenoxy) benzene (APB-133), 3,3 ', 4,4'-diphenyls Combination of hontetracarboxylic dianhydride (DSDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), and (2,2'-bis- (3,4-dicarboxyphenyl) A step selected from the group consisting of a combination of hexafluoropropane dianhydride (6FDA) and 1,3-bis (4-aminophenoxy) benzene (APB-134);
(B) imidizing the first amic acid segment to form a first imidized segment;
(C) reacting the first imidized segment with one or more reactants,
The one or more reactants are (1) with a second acid dianhydride and a second diamine to form a second amic acid segment, and (2) to form a second amic acid segment. Selected from the group consisting of a second amic acid segment and a linking monomer selected from the group consisting of a second acid dianhydride and a second diamine,
The choice of linking monomer between the diamine and dianhydride in (2) above is selected by selecting the linking monomer necessary to produce a polyimide / polyamic acid copolymer having 100% total stoichiometry. The first imidized segment reacts with the one or more reactants to form a segmented polyimide / polyamic acid copolymer comprising a first imidized segment and a second amic acid segment And
The second amic acid segment is linked to the first imidization segment via an amide group having a carbon-nitrogen bond;
The combination of the second acid dianhydride and the second diamine to form the second amic acid segment is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), respectively. And 1,3-bis (4-aminophenoxy) benzene (APB-134), and (3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) and 1,3-bis A segmented polyimide / polyamic acid copolymer prepared by a process selected from the group consisting of a combination with (4-aminophenoxy) benzene (APB-134).   The segmented polyimide / polyamic acid copolymer of claim 1, wherein the one or more reactants are (1) a second acid dianhydride and a second diamine. A segmented melt-processable semicrystal having a stoichiometric amount in the range of 93% to 98% , including a first imidized segment and a second imidized segment having an average molecular weight in the range of 2,000 to 20,000. And the proportion of the second imidized segment in the copolymer is 60 weight percent or more, and the copolymer comprises the following steps:
(A) preparing a first amic acid segment,
A first amic acid segment is a precursor of the first imidized segment and has a first amic acid segment having two identical terminal portions selected from the group consisting of an acid anhydride and an amine A reaction product obtained by reacting the first acid dianhydride with the first diamine at a molecular ratio of
The combination of the first acid dianhydride and the first diamine to form the first amic acid segment is 4,4'-oxydiphthalic anhydride (ODPA) and 1,3-bis (3- In combination with (aminophenoxy) benzene (APB-133), (3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,3-bis (3-aminophenoxy) benzene (APB- 133), a combination of pyromellitic dianhydride (PMDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), (2,2'-bis- (3,4-di) Carboxyphenyl) hexafluoropropane dianhydride (6FDA) in combination with 1,3-bis (3-aminophenoxy) benzene (APB-133), 3,3 ', 4,4'-diphenyls Combination of hontetracarboxylic dianhydride (DSDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), and (2,2'-bis- (3,4-dicarboxyphenyl) A step selected from the group consisting of a combination of hexafluoropropane dianhydride (6FDA) and 1,3-bis (4-aminophenoxy) benzene (APB-134);
(B) imidizing the first amic acid segment to form a first imidized segment;
(C) reacting the first imidized segment with one or more reactants,
The one or more reactants are (1) with a second acid dianhydride and a second diamine to form a second amic acid segment, and (2) to form a second amic acid segment. Selected from the group consisting of a second amic acid segment and a linking monomer selected from the group consisting of a second acid dianhydride and a second diamine,
The choice of linking monomer between the diamine and dianhydride in (2) above is selected by selecting the linking monomer necessary to produce a polyimide / polyamic acid copolymer having 100% total stoichiometry. The first imidized segment reacts with the one or more reactants to form a segmented polyimide / polyamic acid copolymer comprising a first imidized segment and a second amic acid segment And
The second amic acid segment is linked to the first imidization segment via an amide group having a carbon-nitrogen bond;
The combination of the second acid dianhydride and the second diamine to form the second amic acid segment is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), respectively. And 1,3-bis (4-aminophenoxy) benzene (APB-134), and (3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) and 1,3-bis A step selected from the group consisting of a combination with (4-aminophenoxy) benzene (APB-134);
(D) imidating the second amic acid segment to form a second imidized segment;
A segmented melt-processable semi-crystalline polyimide copolymer, characterized in that it is prepared by forming a segmented melt-processable semi-crystalline polyimide copolymer.   The segmented melt-processable semicrystalline polyimide copolymer of claim 3, wherein the one or more reactants are (1) a second acid dianhydride and a second diamine.   The second acid anhydride is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), and the second diamine is 1,3-bis (4-aminophenoxy) benzene ( APB-134), and the combination of the first acid dianhydride and the first diamine to form the first imidized segment is 4,4'-oxydiphthalic anhydride ( ODPA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 1,3-bis Combination with (3-aminophenoxy) benzene (APB-133), combination with pyromellitic dianhydride (PMDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), 2 A combination of 2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), 3,3 ', A combination of 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA) and 1,3-bis (3-aminophenoxy) benzene (APB-133), and 2,2'-bis- (3,4 4. -Dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis (4-aminophenoxy) benzene (APB-134) selected from the group consisting of A segmented melt-processable semicrystalline polyimide copolymer as described in 1.   The first acid anhydride is 4,4′-oxydiphthalic anhydride (ODPA), the first diamine is 1,3-bis (3-aminophenoxy) benzene (APB-133), and The combination of the second acid dianhydride and the second diamine to form the second imidized segment is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA, respectively). ) And 1,3-bis (4-aminophenoxy) benzene (APB-134), and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 1,3-bis 4. A segmented melt-processable semicrystalline polyimide copolymer according to claim 3, selected from the group consisting of combinations with (4-aminophenoxy) benzene (APB-134).   The segmented melt processible semi-finished product of claim 3, wherein the copolymer exhibits a melting point in the range of 330 ° C to 395 ° C and a recoverable semi-crystalline property as determined by differential scanning calorimetry analysis. A crystalline polyimide copolymer.   4. A segmented melt-processable semi-crystalline polyimide copolymer according to claim 3, wherein semi-crystalline segments are present in the copolymer in an amount ranging from 65 to 85 weight percent. The first acid dianhydride is 4,4′-oxydiphthalic anhydride (ODPA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA). And 2,2′-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), wherein the first diamine is 1,3-bis (3-amino) Phenoxy) benzene (APB-133), the second acid dianhydride is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), and the second diamine is 1 , 3-bis (4-aminophenoxy) benzene (APB-134),
The segmented melt-processable semicrystalline polyimide copolymer of claim 3, wherein the first imidized segment has a number average molecular weight in the range of 2,000 to 20,000.